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Vitamin D

(total 699)
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No Structure COMMON NAME NAME DATA No INFORMANT SYMBOL FORMULA MOL.WT(ave) Download BIOOGICAL ACTIVITY PHYSICAL AND CHEMICAL PROPERTIES SPECTRAL DATA CHROMATOGRAM DATA SOURCE CHEMICAL SYNTHESIS METABOLISM GENETIC INFORMATION NOTE REFERENCES
MELTING POINT BOILING POINT DENSITY REFRACTIVE INDEX OPTICAL ROTATION SOLUBILITY UV SPECTRA IR SPECTRA NMR SPECTRA MASS SPECTRA OTHER SPECTRA
1
1a-hydroxy-20-oxo-19,22,23,24,25,26,27-heptanorvitamin D3 / 1a-hydroxy-20-oxo-19,22,23,24,25,26,27-heptanorcholecalciferol
(7E)-(1R,3R)-1,3-dihydroxy-19-nor-9,10-seco-5,7-pregnadien-20-one
VVD0001
Sachiko Yamada
1a-OH-20-oxo-19,22,23,24,25,26,27-heptanor-D3
C20H30O3 318.450 Download ChemDraw structure file
Had no affinity for progesterone receptor in MCF-7. (Ref. 0304)
lmax (EtOH) (nm) 243, 251.5, 261 (Ref. 0304)
1H-NMR (d, CDCl3) 0.51 (3H, s, 18-CH3), 2.14 (3H, s, 21-CH3), 4.06 (1H, m, 3a-H), 4.13 (1H, m, 1b-H), 5.88 (1H, d, J = 11.3 Hz, 7-H), 6.29 (1H, d, J = 11.3 Hz, 6-H) (Ref. 0304)
m/z 318 (M+, 85), 300 (5), 282 (2), 275 (35) 239 (41), 133 (100), 95 (100) (Ref. 0304)



From corresponding C-22 aldehyde via oxidative decarbonylation. (Ref. 0304)



2
20-oxo-22,23,24,25,26,27-hexanorvitamin D3 / 20-oxo-22,23,24,25,26,27-hexanorcholecalciferol
(5Z,7E)-(3S)-3-dihydroxy-9,10-seco-5,7,10(19)-pregnatrien-20-one
VVD0002
Sachiko Yamada
20-oxo-22,23,24,25,26,27-hexanor-D3
C21H30O2 314.462 Download ChemDraw structure file
Had significant affinity for progesterone receptor in MCF-7. (Ref. 0304)
lmax (EtOH) (nm) 264, lmin (nm) 228 (Ref. 0304)
1H-NMR (d, CDCl3) 0.51 (3H, s, 18-CH3), 2.13 (3H, s, 21-CH3), 4.20 (1H, m, 3a-H), 4.45 (1H, m, 1b-H), 4.98 (1H, br s, 19E-H), 5.33 (1H, br s, 19Z-H), 6.04 (1H, d, J = 11.3 Hz, 7-H), 6.36 (1H, d, J = 11.3 Hz, 6-H) (Ref. 0304)
m/z 330 (M+, 31), 312 (21), 183 (95), 134 (100) (Ref. 0304)



From corresponding C-22 aldehyde via oxidative decarbonylation. (Ref. 0304)



3
1a-hydroxy-20-oxo-22,23,24,25,26,27-hexanorvitamin D3 / 1a-hydroxy-20-oxo-22,23,24,25,26,27-hexanorcholecalciferol
(5Z,7E)-(1S,3R)-1,3-dihydroxy-9,10-seco-5,7,10(19)-pregnatrien-20-one
VVD0003
Sachiko Yamada
1a-OH-20-oxo-22,23,24,25,26,27-hexanor-D3
C21H30O3 330.461 Download ChemDraw structure file
Had no affinity for progesterone receptor in MCF-7. (Ref. 0304)
Effects of the compound given at the doses of 0.2 or 1.0mg/kg on the primary immune response in BALB/C mice immunized with 1 times 107 sheep red blood cells were shown in comparison with 1a-hydroxyvitamin D3 (0.2mg/kg). The binding affinity with chick intestinal cytosolic receptor was 1/10,000 compared to 1a,25-(OH)2D3. no calcemic activity of the compound (125mg/kg, times 5, i.v.) was observed. (Ref. 0211)
[a]d-23 9.20 deg (c = 1.00 in EtOH) (Ref. 0211)
lmax (EtOH) (nm) 264, lmin (nm) 228 (Ref. 0304)
1H-NMR (d, CDCl3) 0.51 (3H, s, 18-CH3), 2.13 (3H, s, 21-CH3), 3.95 (1H, m, 3a-H), 4.81 (1H, br s, 19E-H), 5.06 (1H, br s, 19Z-H), 6.06 (1H, d, J = 11.2 Hz, 7-H), 6.22 (1H, d, J = 11.2 Hz, 6-H) (Ref. 0304)
1H-NMR (d, CDCl3) 0.51 (3H, s), 2.13 (3H, s), 2.23-2.37 (1H, m), 2.52-2.73 (3H, m), 2.84 (1H, br d, J = 12.8 Hz), 3.26 (2H, br s), 4.15-4.28 (1H, br), 4.36-4.47 (1H, br), 4.99 (1H, t, J = 1.4 Hz), 5.33 (1H, t, J = 1.4 Hz), 6.04 (1H, d, J = 11.4 Hz), 6.36 (1H, d, J = 11.4 Hz) (Ref. 0211)
m/z 314 (M+, 23), 296 (2.4), 281 (15), 271 (1.5) 253 (4.6), 136 (33), 118 (73), 43 (100) (Ref. 0304)
HRMS Calcd 330.2195, Found 330.2176 (Ref. 0211)


From corresponding C-22 aldehyde via oxidative decarbonylation. (Ref. 0304)
Synthesis from dehydroepiandrostertone via 5,7-diene compound by photochemical method. (Ref. 0211)



4
1a,21-dihydroxy-20-oxo-22,23,24,25,26,27-hexanorvitamin D3 / 1a,21-dihydroxy-20-oxo-22,23,24,25,26,27-hexanorcholecalciferol
(5Z,7E)-(1S,3R)-1,3,21-trihydroxy-9,10-seco-5,7,10(19)-pregnatrien-20-one
VVD0005
Sachiko Yamada
1a,21-(OH)2-20-oxo-22,23,24,25,26,27-hexanor-D3
C21H30O4 346.460 Download ChemDraw structure file
The binding affinity for chick intestinal cytosolic receptor was less than 1/100,000 compared to 1a,25-(OH)2D3. (Ref. 0211)
[a]d-23 2.81 deg (c = 0.07 in EtOH) (Ref. 0211)
lmax (EtOH) (nm) 262 (Ref. 0211)
1H-NMR (d, CDCl3) 0.53 (3H, s), 2.52-2.68 (2H, m), 2.87 (1H, d, J = 12.0 Hz), 3.26 (2H, br s), 4.12-4.34 (3H, m), 4.38-4.49 (1H, m), 4.98 (1H, t, J = 1.7 Hz), 5.33 (1H, t, J = 1.7 Hz), 6.05 (1H, d, J = 10.8 Hz), 6.34 (1H, d, J = 10.8 Hz) (Ref. 0211)
m/z 346 (M+), 134 (100%) (Ref. 0211)
HRMS Calcd 346.2144, Found 346.2146 (Ref. 0211)


Synthesis from dehydroepiandrostertone via 5,7-diene compound by photochemical method. (Ref. 0211)



5
1a,17a,21-trihydroxy-20-oxo-22,23,24,25,26,27-hexanorvitamin D3 / 1a,17a,21-trihydroxy-20-oxo-22,23,24,25,26,27-hexanorcholecalciferol
(5Z,7E)-(1S,3R,17R)-1,3,17,21-tetrahydroxy-9,10-seco-5,7,10(19)-pregnatrien-20-one
VVD0006
Sachiko Yamada
1a,17a,21-(OH)3-20-oxo-22,23,24,25,26,27-hexanor-D3
C21H30O5 362.460 Download ChemDraw structure file
The binding affinity for chick intestinal cytosolic receptor was less than 1/100,000 compared to 1a,25-(OH)2D3. (Ref. 0211)
lmax (EtOH) (nm) 264 (Ref. 0211)
1H-NMR (d, CDCl3) 0.58 (3H, s), 2.35 (1H, dd, J = 12.5 and 6.3 Hz), 2.55-2.96 (4H, m), 3.10 (1H, t, J = 4.9 Hz), 4.21-4.31 (1H, m), 4.35 (1H, dd, J = 20.0 and 4.9 Hz), 4.38-4.51 (1H, m), 4.66 (1H, t, J = 20.0 and 4.9 Hz), 5.01 (1H, t, J = 1.5 Hz), 5.35 (1H, t, J = 1.5 Hz), 6.09 (1H, d, J = 11.4 Hz), 6.38 (1H, d, J = 11.4 Hz) (Ref. 0211)




Synthesis from dehydroepiandrostertone via 5,7-diene compound by photochemical method. (Ref. 0211)



6
(20S)-1a,20-dihydroxy-22,23,24,25,26,27-hexanorvitamin D3 / (20S)-1a,20-dihydroxy-22,23,24,25,26,27-hexanorcholecalciferol
(5Z,7E)-(1S,3R,20S)-9,10-seco-5,7,10(19)-pregnatriene-1,3,20-triol
VVD0007
Sachiko Yamada
1a,20S-(OH)2-22,23,24,25,26,27-hexanor-D3
C21H32O3 332.477 Download ChemDraw structure file
The antiproliferation activity towards HL-60 was <1/217 of 22-oxacalcitriol (OCT). The binding affinity for bovine thymus vitamin D receptor was 1/929 of OCT. (Ref. 0213)
[a]d-20 55.10 deg (c = 0.01 in EtOH) (Ref. 0212)
lmax (EtOH) (nm) 263, lmin (nm) 227 (Ref. 0212)
(neat) 3375, 2920, 2865, 1050 cm-1 (Ref. 0212)
1H-NMR (d, CDCl3) 0.55 (3H, s), 1.23 (3H, d, J = 6.6 Hz), 2.33 (1H, dd, J = 6.0 and 13.1 Hz), 2.61 (1H, dd, J = 2.9 and 13.1 Hz), 2.85 (1H, dd, J = 2.9 and 10.8 Hz), 3.25-3.57 (4H, m), 3.62-3.76 (1H, m), 4.17-4.31 (1H, m), 4.37-4.51 (1H, m), 5.00 (1H, s), 5.33 (1H, s), 6.04 (1H, d, J = 11.7 Hz), 6.37 (1H, d, J = 11.7Hz) (Ref. 0212)
m/z 332 (M+), 134 (100%) (Ref. 0212)
Colorless foam. (Ref. 0213)
HRMS Calcd 332.2351, Found 332.2369 (Ref. 0212)
1)Flash column chromatography with CH2Cl2-EtOH (10 : 1). 2)Fash column chromatography with AcOEt. 3)Flash column chromatography with CH2Cl2-EtOH (10 : 1). (Ref. 0213)

Synthesis from dehydroepiandrostertone via the 5,7-diene by photochemical method. (Ref. 0212/0213)



7
1a-hydroxy-22-oxo-23,24,25,26,27-pentanorvitamin D3 / 1a-hydroxy-22-oxo-23,24,25,26,27-pentanorcholecalciferol
(5Z,7E)-(1S,3R)-1,3-dihydroxy-9,10-seco-23,24-dinor-5,7,10(19)-cholatrien-22-one
VVD0008
Sachiko Yamada
1a-OH-22-oxo-pentanor-D3
C22H32O3 344.488 Download ChemDraw structure file
HL-60 human promyelocytes differentiation: ED50 in nitro blue tetrazplium reduction, phagocytic activity, and nonspecific acid esterase activity are 7.5 times 10-7 M, 8.2 times 10-7 M and 8.5 times 10-7 M, respectively, when 1,25-(OH)2D3 shows the respective ED50 values of 1.0 times 10-8 M, 1.0 times 10-8 M and 1.1 times 10-8 M, respectively. (Ref. 0228)





From C(22) ester precursor. (Ref. 0228)



8
(6RS)-22-oxo-23,24,25,26,27-pentanorvitamin D3 6,19-sulfur dioxide adduct / (6RS)-22-oxo-23,24,25,26,27-pentanorcholecalciferol 6,19-sulfur dioxide adduct
(7E)-(3S,6RS)-3-hydroxy-6,19-epithio-23,24-dinor-9,10-seco-5(10),7-choladien-22-al S,S-dioxide
VVD0009
Sachiko Yamada
22-oxo-23,24,25,26,27-pentanor-D3 6,19-sulfur dioxide adduct
C22H32O4S 392.553 Download ChemDraw structure file

1H-NMR (d, CDCl3) (a 1:1 mixture of C6) epimers) 0.62 and 0.70 (1:1, 3 H, s, H-18), 1.14 and 1.15 (1:1, 3 H, d, J = 6.9 Hz, H-21), 3.68 (2 H, br, H-19), 4.09 (1 H, m, H-3), 4.57 and 4.66 (1:1, 1 H, d, J = 9.9 Hz, H-6), 4.76 and 4.79 (1:1, 1 H, d, J = 9.9 Hz, H-7), 9.58 and 9.60 (1:1, 1H, d, J = 3.0 Hz, CHO). (Ref. 0334)




From vitamin D2 sulfur dioxide adduct by ozonolysis. (Ref. 0334)



9
1a-hydroxy-23,24,25,26,27-pentanorvitamin D3 / 1a-hydroxy-23,24,25,26,27-pentanorcholecalciferol
(5Z,7E)-(1S,3R)-23,24-dinor-9,10-seco-5,7,10(19)-cholatriene-1,3-diol
VVD0010
Sachiko Yamada
1a-OH-23,24,25,26,27-pentanor-D3
C22H34O2 330.504 Download ChemDraw structure file
HL-60 human promyelocytes differentiation : ED50 in nitro blue tetrazolium reduction, phagocytic activity, and nonspecific acid esterase activity are 1.8 times 10-7 M, 1.9 times 10-7 M and 1.7 times 10-7 M, respectively, when 1,25-(OH)2D3 shows the respective ED50 values of 1.0 times 10-8 M, 1.0 times 10-8 M and 1.1 times 10-8 M, respectively. (Ref. 0228)





Prepared via 3,5-cyclovitamin D intermediate. (Ref. 0228)



10
22-hydroxy-23,24,25,26,27-pentanorvitmin D3 / 22-hydroxy-23,24,25,26,27-pentanorcholecalciferol
(5Z,7E)-(3S)-23,24-dinor-9,10-seco-5,7,10(19)-cholatrien-3-ol
VVD0011
Sachiko Yamada
22-OH-23,24,25,26,27-pentanor-D3
C22H34O2 330.504 Download ChemDraw structure file






From vitamin D2 via ozonolysis of its sulfur dioxide adduct. (Ref. 0334)



11
1a,22-dihydroxy-23,24,25,26,27-pentanorvitamin D3 / 1a,22-dihydroxy-23,24,25,26,27-pentanorcholecalciferol
(5Z,7E)-(1S,3R)-23,24-dinor-9,10-seco-5,7,10(19)-cholatriene-1,3,22-triol
VVD0012
Sachiko Yamada
1a,22-(OH)2-23,24,25,26,27-pentanor-D3
C22H34O3 346.504 Download ChemDraw structure file
HL-60 human promyelocytes differentiation : ED50 in nitro blue tetrazolium reduction, phagocytic activity, and nonspecific acid esterase activity are 1.4 times 10-6 M, 1.8 times 10-6 M and 2.0 times 10-6 M, respectively, when 1,25-(OH)2D3 shows the respective ED50 values of 1.0 times 10-8 M, 1.0 times 10-8 M and 1.1 times 10-8 M, respectively. (Ref. 0228)





From C(22) ester precursor. (Ref. 0228)



12
(6RS)-22-hydroxy-23,24,25,26,27-pentanorvitamin D3 6,19-sulfur dioxide adduct / (6RS)-22-hydroxy-23,24,25,26,27-pentanorcholecalciferol 6,19-sulfur dioxide adduct
(7E)-(3S,6RS)-6,19-epithio-23,24-dinor-9,10-seco-5(10),7-choladiene-3,22-diol S,S-dioxide
VVD0013
Sachiko Yamada
22-OH-23,24,25,26,27-pentanor-D3 6,19-sulfur dioxide adduct
C22H34O4S 394.569 Download ChemDraw structure file

1H-NMR (d, CDCl3, 270MHz) 0.59 and 0.68 (1:1) (3H, s, 18-H), 1.07 (3H, d, J = 6.4 Hz, 21-H), 3.67 (2H, m, 19-H), 4.11 (1H, m, 3-H) (Ref. 0334)




From vitamin D2 sulfur dioxide adduct by ozonolysis followed by reduction. (Ref. 0334)



13
1a-hydroxy-24,25,26,27-tetranorvitamin D3 23-carboxylic acid / calcitroic acid
(5Z,7E)-(1S,3R)-1,3-dihydroxy-24-nor- 9,10-seco-5,7,10(19)-cholatrien-23-oic acid
VVD0014
Sachiko Yamada
1a-OH-24,25,26,27-tetranor-D3 23-carboxylic acid
C23H34O4 374.514 Download ChemDraw structure file
Bone Mineral Mobilization and Intestinal Calcium Transport Activity of Calcitroic Acid. (Ref. 0072)
122-126 degC (Ref. 0074)
lmax (nm) (emax) 262 (18000), lmin (nm) (emin) 226 (10000) (Ref. 0074)
Me-ester : lmax (nm) (emax) 264 (18000) (Ref. 0071)
1H-NMR (d, CDCl3) 6.43, 6.06 (2H, ABq, J = 11 Hz, 6-, 7-H), 5.56 (1H, br s, 19E-H), 5.04 (1H, br s, 19Z-H), 4.46 (1H, m, 1b-H), 4.26 (1H, m, 3a-H), 2.80 (1H, m, 9b-H), 0.99 (3H, d, J = 6 Hz, 21-H), 0.59 (3H, s, 18-H) (Ref. 0074)
Me-ester : 1H-NMR (d, CDCl3) 0.58 (3H, s, 18-CH3), 0.99 (3H, d, J = 5.9 Hz, 21-CH3), 3.67 (3H, s, COOCH3), 4.23 (1H, m, 3a-H), 4.43 (1H, m, 1b-H), 5.00 (1H, s, 19(Z)-H), 5.33 (1H, s, 19(E)-H), 6.02 (1H, d, J = 11.0 Hz, 7-H), 6.38 (1H, d, J = 11.0 Hz, 6-H) (Ref. 0071)
Me-ester : m/z 388, 370, 352 , 152, 134, 287, 269, 251. Spectrum (Ref. 0070)

HPLC : (Ref. 0070/0073)
Isolation from rat liver. (Ref. 0070)
Isolation and identification from vitamin D supplemented rat kidney homogenates incubated with 24,25-(OH)2D3. (Ref. 0118)
From C(22)-steroid carboxylic acid via one-carbon homologation, conversion to tetranor-vitamin D3 23-carboxylic acid and 1a-hydroxylation of the corresponding 3,5-cyclovitamin D. (Ref. 0071)
From 3b-acetoxypregn-7-ene-22-carboxaldehyde. (Ref. 0074)
A final catabolite produced from the active vitamin D3 metabolite, 1,25-(OH)2D3, via 24-hydroxylation pathway.(Ref. 0034/0065/0066/0067/0068/0069/0070/0073)


14
1a-hydroxy-24,25,26,27-tetranorvitamin D3 / 1a-hydroxy-24,25,26,27-tetranorcholecalciferol
(5Z,7E)-(1S,3R)-24-nor-9,10-seco-5,7,10(19)-cholatriene-1,3-diol
VVD0015
Sachiko Yamada
1a-OH-23,24,25,26,27-tetranor-D3
C23H36O2 344.531 Download ChemDraw structure file
HL-60 human promyelocytes differentiation : ED50 in nitro blue tetrazolium reduction, phagocytic activity, and nonspecific acid esterase activity are 2.3 times 10-7 M, 2.5 times 10-7 M and 2.7 times 10-7 M, respectively, when 1,25-(OH)2D3 shows the respective ED50 values of 1.0 times 10-8 M, 1.0 times 10-8 M and 1.1 times 10-8 M, respectively. (Ref. 0228)





Prepared via 3,5-cyclovitamin D intermediate. (Ref. 0228)



15
(22R)-22-hydroxy-24,25,26,27-tetranorvitmin D3 / (22R)-22-hydroxy-24,25,26,27-tetranorcholecalciferol
(5Z,7E)-(3S,22R)- 24-nor-9,10-seco-5,7,10(19)-cholatriene-3,22-diol
VVD0016
Sachiko Yamada
22R-OH-24,25,26,27-tetranor-D3
C23H36O2 344.531 Download ChemDraw structure file

1H-NMR (d, CDCl3, 270MHz) 0.57 (3H, s, 18-H), 0.93 (3H, d, J = 6.6 Hz, 21-H), 1.04 (3H, d, J = 6.6 Hz, 23-H), 3.93 (2H, m, 3- and 22-H), 4.82 and 5.05 (each 1H, m, 19-H), 6.04 and 6.23 (each 1H, d, J = 11.5 Hz, 6- and 7-H) (Ref. 0334)




From vitamin D2 sulfur dioxide adduct via ozonolysis followed by Grignard reaction. (Ref. 0334)



16
(22S)-22-hydroxy-24,25,26,27-tetranorvitmin D3 / (22S)-22-hydroxy-23,24,25,26,27-pentanorcholecalciferol
(5Z,7E)-(3S,22S)- 24-nor-9,10-seco-5,7,10(19)-cholatriene-3,22-diol
VVD0017
Sachiko Yamada
22S-OH-24,25,26,27-tetranor-D3
C23H36O2 344.531 Download ChemDraw structure file

(EtOH) lmax (nm) 265, lmin (nm) 212 (Ref. 0334)
1H-NMR (d, CDCl3, 270MHz) 0.55 (3H, s, 18-H), 0.93 (3H, d, J = 6.9 Hz, 21-H), 1.16 (3H, d, J = 6.4 Hz, 23-H), 3.95 (2H, m, 3- and 22-H), 4.82 and 5.05 (each 1H, m, 19-H), 6.04 and 6.23 (each 2H, d, J = 11.4 Hz, 6- and 7-H) (Ref. 0334)
m/z 344 (M+, 75.7), 326 (93.7), 311 (23.6), 271 (15.6), 253 (41.1), 136 (96.7), 118 (100) (Ref. 0334)



From vitamin D2 sulfur dioxide adduct via ozonolysis followed by Grignard reaction. (Ref. 0334)



17
(5E)-(22R)-22-hydroxy-24,25,26,27-tetranorvitmin D3 / (5E)-(22R)-22-hydroxy-24,25,26,27-tetranorcholecalciferol
(5E,7E)-(3S,22R)- 24-nor-9,10-seco-5,7,10(19)-cholatriene-3,22-diol
VVD0018
Sachiko Yamada
(5E)-22R-OH-24,25,26,27-tetranor-D3
C23H36O2 344.531 Download ChemDraw structure file

1H-NMR (d, CDCl3, 270MHz) 0.59 (3H, s, 18-H), 0.93 (3H, d, J = 6.6 Hz, 21-H), 1.04 (3H, d, J = 6.3 Hz, 23-H), 3.89 (1H, m, 3-H), 3.93 (1H, m, 22-H), 4.69 and 4.98 (each 1H, s, 19-H), 5.88 and 6.54 (each 1H, d, J = 11.6 Hz, 6- and 7-H) (Ref. 0334)
m/z 344 (M+, 63.4), 326 (100), 308 (23.1), 271 (14.2), 253 (40.0), 251 (37.5) (Ref. 0334)



From vitamin D2 sulfur dioxide adduct via ozonolysis followed by Grignard reaction. (Ref. 0334)



18
(5E)-(22S)-22-hydroxy-24,25,26,27-tetranorvitmin D3 / (5E)-(22S)-22-hydroxy-24,25,26,27-tetranorcholecalciferol
(5E,7E)-(3S,22S)- 24-nor-9,10-seco-5,7,10(19)-cholatriene-3,22-diol
VVD0019
Sachiko Yamada
(5E)-22S-OH-24,25,26,27-tetranor-D3
C23H36O2 344.531 Download ChemDraw structure file

1H-NMR (d, CDCl3, 270MHz) 0.57 (3H, s, 18-H), 0.93 (3H, d, J = 6.8 Hz, 21-H), 1.17 (3H, d, J = 6.4 Hz, 23-H), 3.89 (1H, m, 3-H), 3.97 (1H, dq, J = 6.4 and 1.4 Hz, 22-H), 4.69 and 4.98 (each 1H, s, 19-H), 5.88 and 6.55 (each 1H, d, J = 11.6 Hz, 6- and 7-H) (Ref. 0334)
m/z 344 (M+, 63.4), 326 (100), 308 (23.1), 271 (14.2), 253 (40.0), 251 (37.5) (Ref. 0334)



From vitamin D2 sulfur dioxide adduct via ozonolysis followed by Grignard reaction. (Ref. 0334)



19
23-hydroxy-24,25,26,27-tetranorvitamin D3 / 23-hydroxy-24,25,26,27-tetranorcholecalciferol
(5Z,7E)-(3S)-24-nor-9,10-seco-5,7,10(19)-cholatriene-3,23-diol
VVD0020
Sachiko Yamada
23-OH-24,25,26,27-tetranor-D3
C23H36O2 344.531 Download ChemDraw structure file


m/z 344 (M+), 326, 311, 285, 271, 253, 211, 136, 118. Spectrum (Ref. 0105)

HPLC : (Ref. 0105)
Isolation and identification : By perfusing kidneys from vitamin D3 replete rats with 24,25-(OH)2D3. (Ref. 0105)
From 22-bromo-23,24-dinor-5,7-choladien-3-ol ether via one carbon homologation and photochemical transformation. (Ref. 0105)



20
1a,23-dihydroxy-24,25,26,27-tetranorvitamin D3 / 1a,23-dihydroxy-24,25,26,27-tetranorcholecalciferol
(5Z,7E)-(1S,3R)-24-nor-9,10-seco-5,7,10(19)-cholatriene-1,3,23-triol
VVD0021
Sachiko Yamada
1a,23-(OH)2-24,25,26,27-tetranor-D3
C23H36O3 360.530 Download ChemDraw structure file
HL-60 human promyelocytes differentiation : ED50 in nitro blue tetrazolium reduction, phagocytic activity, and nonspecific acid esterase activity are 3.0 times 10-6 M, 2.0 times 10-6 M and 2.0 times 10-6 M, respectively, when 1,25-(OH)2D3 shows the respective ED50 values of 1.0 times 10-8 M, 1.0 times 10-8 M and 1.1 times 10-8 M, respectively. (Ref. 0228)
lmax (nm) 265, lmin (nm) 228 (Ref. 0069)

tris-TMS-ether: Spectrum (Ref. 0069)

HPLC : (Ref. 0069)

From 1,23,25-(OH)3-24-oxo-D3, which was produced enzymatically from 1,24,25-(OH)3D3, by NaIO4 oxidation followed by NaBH4 reduction. (Ref. 0069)
1,23-(OH)2-Tetranor-D3 is metabolized to 1-OH-tetranor-D3 23-carboxylic acid (calcitroic acid). (Ref. 0070/0073)


21
cholacalcioic acid / 25,26,27-trinorvitamin D3 24-carboxylic acid / 25,26,27-trinorcholecalciferol 24-carboxylic acid
(5Z,7E)-(3S)-3-hydroxy-9,10-seco-5,7,10(19)-cholatrien-24-oic acid
VVD0022
Sachiko Yamada
25,26,27-trinor-D3 24-carboxylic acid
C24H36O3 372.541 Download ChemDraw structure file

Me-ester : lmax (nm) 264, lmin (nm) 229 (Ref. 0118)

Me-ester : m/z 386 (M+), 368, 327, 353, 271, 253, 136, 118 (Ref. 0118)


Isolation and identification from vitamin D supplemented rat kidney homogenates incubated with 24,25-(OH)2D3. (Ref. 0118)




22
1a-hydroxy-25,26,27-trinorvitamin D3 24-carboxylic acid
(5Z,7E)-(1S,3R)-1,3-dihydroxy-9,10-seco-5,7,10(19)-cholatrien-24-oic acid
VVD0023
Sachiko Yamada
1a-OH-25,26,27-trinor-D3 24-carboxylic acid
C24H36O4 388.540 Download ChemDraw structure file

117-120 degC (Ref. 0074)
lmax (nm) (e) 263 (18200) , lmin (nm) (e) 227 (10400) (Ref. 0074)
1H-NMR (d, CDCl3) 6.42, 6.04 (2H, ABq, J = 11.6 Hz, 6-, 7-H), 5.35 (1H, bs, 19E-H), 5.03 (1H, bs, 19Z-H), 4.46 (1H, m, 1b-H), 4.25 (1H, m, 3a-H), 2.80 (1H, m, 9b-H), 0.95 (3H, d, J = 5.5 Hz, 21-H), 0.55 (3H, s, 18-H) (Ref. 0074)




From methyl-3b-hydroxy-chola-1,5,7-triene-24-oate. (Ref. 0074)



23
1a,24-dihydroxy-25,26,27-trinorvitamin D3 / 1a,24-dihydroxy-25,26,27-trinorcholecalciferol
(5Z,7E)-(1S,3R)-9,10-seco-5,7,10(19)-cholatriene-1,3,24-triol
VVD0024
Sachiko Yamada
1a,24-(OH)2-25,26,27-trinor-D3
C24H38O3 374.557 Download ChemDraw structure file
HL-60 human promyelocytes differentiation : ED50 in nitro blue tetrazolium reduction, phagocytic activity, and nonspecific acid esterase activity are 7.0 times 10-7 M, 6.0 times 10-7 M and 1.0 times 10-6 M, respectively, when 1,25-(OH)2D3 shows the respective ED50 values of 1.0 times 10-8 M, 1.0 times 10-8 M and 1.1 times 10-8 M, respectively. (Ref. 0228)









24
26,26,26-trifluoro-25-hydroxy-27-norvitamin D3 / 26,26,26-trifluoro-25-hydroxy-27-norcholecalciferol
(5Z,7E)-(3S)-26,26,26-trifluoro-27-nor-9,10-seco-5,7,10(19)-cholestatriene-3,25-diol
VVD0025
Sachiko Yamada
26,26,26-F3-25-OH-27-nor-D3
C25H37F3O2 426.555 Download ChemDraw structure file

lmax (nm) 264, lmin (nm) 228 (Ref. 0201)

m/z 440 (M+), 425, 422, 408, 271, 253, 136, 118 (Ref. 0201)







25
1a-hydroxy-26,27-dinorvitamin D3 25-carboxylic acid / 1a-hydroxy-26,27-dinorcholecalciferol 25-carboxylic acid
(5Z,7E)-(1S,3R)-1,3-dihydroxy-25-homo-9,10-seco-5,7,10(19)-cholatrien-25-oic acid
VVD0026
Sachiko Yamada
1a-OH-26,27-dinor-D3 25-carboxylic acid
C25H38O4 402.567 Download ChemDraw structure file

97-101 degC (Ref. 0074)
lmax (nm) (e) 264 (18300) , lmin (nm) (e) 228 (10300) (Ref. 0074)
1H-NMR (d, CDCl3) 6.42, 6.04 (2H, ABq, J = 11.6 Hz, 6-, 7-H), 5.35 (1H, br s, 19E-H), 5.03 (1H, br s, 19Z-H), 4.45 (1H, m, 1b-H), 4.25 (1H, m, 3a-H), 2.81 (1H, m, 9b-H) (Ref. 0074)
m/z 416 (M+), 398 (M+-H2O), 380 (M+-2H2O), 269, 251, 134, 105 (Ref. 0074)



From methyl-3b-hydroxy-25-homo-chola-1,5,7-trien-25-oate. (Ref. 0074)



26
1a-hydroxy-21-nor-20-oxavitamin D3 / 1a-hydroxy-21-nor-20-oxacholecalciferol
(5Z,7E)-(1S,3R)-21-nor-20-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0027
Sachiko Yamada
1a-OH-20-oxa-21-nor-D3
C25H40O3 388.583 Download ChemDraw structure file

[a]d-24 -30.2 deg (c = 0.86 in EtOH) (Ref. 0207)
(EtOH) lmax (nm) 262, lmin (nm) 227 (Ref. 0207)
1H-NMR (d, CDCl3) 0.62 (3H, s), 0.86 (3H, d, J = 0.8 Hz), 0.89 (3H, d, J = 0.8 Hz), 3.35-3.56 (3H, m), 4.15-4.32 (1H, m), 4.38-4.51 (1H, m), 5.00 (1H, t, J = 1.6 Hz), 5.32 (1H, t, J = 1.6 Hz), 6.00 (1H, d, J = 12.0 Hz), 6.38 (1H, d, J = 12.0 Hz) (Ref. 0207)
m/z 388 (M+), 134 (100%) (Ref. 0207)
Colorless crystals (Ref. 0207)


Synthesis from dehydroepiandrostertone via 5,7-diene compound by photochemical method. (Ref. 0207)



27
1a,25-dihydroxy-23,24-dinorvitamin D3 / 1a,25-dihydroxy-23,24-dinorcholecalciferol
(5Z,7E)-(1S,3R)-23,24-dinor-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0028
Sachiko Yamada
1a,25-(OH)2-23,24-dinor-D3
C25H40O3 388.583 Download ChemDraw structure file
HL-60 human promyelocytes differentiation : ED50 in nitro blue tetrazolium reduction, phagocytic activity and nonspecific acid esterase activity are 2.4 times 10-6 M, 2.0 times 10-6 M and 2.1 times 10-6 M respectively, when 1,25-(OH)2D3 shows the respective ED50 values of 1.0 times 10-8 M, 1.0 times 10-8 M and 1.1 times 10-8 M respectively. (Ref. 0228)









28
1a,25-dihydroxy-26,27-dinorvitamin D3 / 1a,25-dihydroxy-26,27-dinorcholecalciferol
(5Z,7E)-(1S,3R)-26,27-dinor-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0029
Sachiko Yamada
1a,25-(OH)2-26,27-dinor-D3
C25H40O3 388.583 Download ChemDraw structure file
HL-60 human promyelocytes differentiation : ED50 in nitro blue tetrazolium reduction, phagocytic activity, and nonspecific acid esterase activity are 1.0 times 10-6 M, 1.2 times 10-6 M and 1.0 times 10-6 M, respectively, when 1,25-(OH)2D3 shows the respective ED50 values of 1.0 times 10-8 M, 1.0 times 10-8 M and 1.1 times 10-8 M, respectively. (Ref. 0228)









29
1a,25-dihydroxy-21-nor-20-oxavitamin D3 / 1a,25-dihydroxy-21-nor-20-oxacholecalciferol
(5Z,7E)-(1S,3R)-21-nor-20-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0030
Sachiko Yamada
1a,25-(OH)2-20-oxa-21-nor-D3
C25H40O4 404.583 Download ChemDraw structure file
Differentiation inducing activity of HL-60 (ED50): 4.0 times 10-8 M (1,25-(OH)2D3, 8.3 times 10-9 M); Binding affinity for chick intestinal receptor: 1/1000 of 1,25-(OH)2D3. Calcemic activity at a dose of 500mg/kg in normal mice, 8.96 pm 0.13 (1.25-(OH)2D3, 11.04 pm 0.12 at 10mg/kg). (Ref. 0209)
[a]d-24 -44.6 deg (c = 0.56 in EtOH) (Ref. 0207)
lmax (EtOH) (nm) 262, lmin (nm) 227 (Ref. 0207)
1H-NMR (d, CDCl3) 0.63 (3H, s), 1.23 (6H, s), 3.51 (3H, m), 4.17-4.29 (1H, m), 4.34-4.49 (1H, m), 4.98 (1H, t, J = 1.6 Hz), 5.31 (1H, t, J = 1.6 Hz), 5.99 (1H, d, J = 12.0 Hz), 6.36 (1H, d, J = 12.0 Hz) (Ref. 0207)
m/z 404 (M+), 83 (100%) (Ref. 0207)
Colorless crystals (Ref. 0207)


Synthesis from dehydroepiandrostertone via 5,7-diene compound by photochemical method. (Ref. 0209)



30
1a,25-dihydroxy-24-nor-22-oxavitamin D3 / 1a,25-dihydroxy-24-nor-22-oxacholecalciferol
(5Z,7E)-(1S,3R)-24-nor-22-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0031
Sachiko Yamada
1a,25-(OH)2-22-oxa-24-nor-D3
C25H40O4 404.583 Download ChemDraw structure file
The activity inducing differentiation of human myeloid leukemia cells (HL-60) into macrophases in vitro was compared with 1,25-(OH)2D3. Figure (Ref. 0203)
(EtOH) lmax (nm) 263, lmin (nm) 227(Ref. 0203)
1H-NMR (d, CDCl3) 0.53 (3H, s), 1.16 (3H, d, J = 6.2 Hz), 1.19 (6H, s), 3.04 (1H, d, J = 8.4 Hz), 3.24-3.48 (1H, br), 3.39 (1H, d, J = 8.4 Hz), 4.20-4.32 (1H, br), 4.40-4.52 (1H, br), 4.99 (1H, s), 5.33 (1H, s), 6.03 (1H, d, J = 11.4 Hz), 6.37 (1H, d, J = 11.4 Hz) (Ref. 0203)
m/z 404 (M+), 72 (100%) (Ref. 0203)
Colorless foam. (Ref. 0203)
1)Flash column chromatography with CH2Cl2/EtOH (12.5 : 1), 2)Flash column chromatography with AcOEt/n-hexane (6 : 1), 3)Preparative TLC developed four times with CH2Cl2/EtOH (12.5 : 1) (Ref. 0203)

Synthesis from dehydroepiandrostertone via 1a,3b-dihydroxy-20(S)-(2-hydroxy-2-methylpropyloxy)pregna-5,7-diene by photochemical method. (Ref. 0203)



31
1a-hydroxy-24-methylsulfonyl-25,26,27-trinorvitamin D3 / 1a-hydroxy-24-methylsulfonyl-25,26,27-trinorcholecalciferol
(5Z,7E)-(1S,3R)-24-methylsulfonyl-9,10-seco-5,7,10(19)-cholatriene-1,3-diol
VVD0032
Sachiko Yamada
24-methylsulfonyl-1a-OH-25,26,27-trinor-D3
C25H40O4S 436.649 Download ChemDraw structure file

1H-NMR (d, CD2Cl2) 6.34 and 5.98 (2H, AB pattern, J = 11.2 Hz, 6- and 7-H), 5.29 (1H, br s, 19E-H), 4.94 (1H, br s, 19Z-H), 4.35 (1H, m, 1-H), 4.15 (1H, m, 3-H), 2.88 - 2.97 (2H, m, 24-H), 2.84 (3H, s, SO2CH3), 0.94 (3H, d, J = 6.4 Hz, 21C-CH3), 0.53 (3H, s, 18C-CH3) (Ref. 0195)
13C-NMR (d, CD2Cl2) 148.6 (C), 143.2 (C), 134.1 (C), 125.0 (CH), 117.0 (CH), 111.8 (C-19), 71.2 (CH), 67.2 (CH), 56.7, 56.6, 55.7, 53.5, 46.3, 45.8, 43.4, 40.9, 36.2, 35.0, 29.4, 28.0, 23.9, 22.6, 19.7, 18.8, 12.1 (Ref. 0195)








32
1,25-dihydroxy-2,4-dinor-1,3-secovitamin D3 / 1,25-dihydroxy-2,4-dinor-1,3-secocholecalciferol
(5Z,7E)-A-dinor-(1,2)-(9,10)-diseco-5,7,10(19)-cholestatriene-1,2,25-triol
VVD0034
Sachiko Yamada
1,25-(OH)2-2,4-dinor-1,3-seco-D3
C25H42O3 390.599 Download ChemDraw structure file
Affinity for chick intestinal receptor: 2% of 1,25-(OH)2D3 effect. (Ref. 0359)









33
25,26-epoxy-1a-hydroxy-23,23,24,24-tetradehydro-19-norvitamin D3 / 25,26-epoxy-1a-hydroxy-23,23,24,24-tetradehydro-19-norcholecalciferol
(7E)-(1R,3R)-25,26-epoxy-19-nor-9,10-seco-5,7-cholestadien-23-yne-1,3-diol
VVD0035
Sachiko Yamada
25,26-epoxy-1a-OH-23,23,24,24-tetradehydro-19-nor-D3
C26H38O3 398.578 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for pig intestinal receptor and human vitamin D binding protein : 20% and 1%, respectively. Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60), osteosarcoma (MG-63), and breast carcinoma (MCF-7) cells : 12%, 4% and 20%, respectively. Elevation of serum calcium, serum osteocalcin, bone calcium, and duodenal calbindin in rachitic chicks : all < 1%. (Ref. 0240)





By epoxidation of the corresponding olefinic precursor which was constructed from Inhoffen-Lythgoe diol. (Ref. 0240)



34
(22E,24E)-1a,26-dihydroxy-22,23,24,25-tetradehydro-27-norvitamin D3 / (22E,24E)-1a,26-dihydroxy-22,23,24,25-tetradehydro-27-norcholecalciferol
(5Z,7E,22E,24E)-(1S,3R)-27-nor-9,10-seco-5,7,10(19),22,24-cholestapentaene-1,3,26-triol
VVD0036
Sachiko Yamada
(22E,24E)-1a,26-(OH)2-22,23,24,25-tetradehydro-27-nor-D3
C26H38O3 398.578 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of U937 cells, < 80% ; Induction of differentiation of U 937 cells, < 5%. (Ref. 0288>





From protected (5E)-1a-hydroxy-22-oxo-23,24,25,26,27-pentanorvitamin D3 via side chain introduction by Wittig reaction, reduction, photoisomerization and deprotection. (Ref. 0288)



35
(17E)-1a,25-dihydroxy-17,20-didehydro-21-norvitamin D3 / (17E)-1a,25-dihydroxy-17,20-didehydro-21-norcholecalciferol
(5Z,7E,17E)-(1S,3R)-21-nor-9,10-seco-5,7,10(19),17-cholestatetraene-1,3,25-triol
VVD0037
Sachiko Yamada
(17E)-1a,25-(OH)2-17,20-didehydro-21-nor-D3
C26H40O3 400.594 Download ChemDraw structure file






From 4-hydroxyhydrindanone via introduction of the side chain and A-ring fragments. (Ref. 0315)



36
(17Z)-1a,25-dihydroxy-17,20-didehydro-21-norvitamin D3 / (17Z)-1a,25-dihydroxy-17,20-didehydro-21-norcholecalciferol
(5Z,7E,17Z)-(1S,3R)-21-nor-9,10-seco-5,7,10(19),17-cholestatetraene-1,3,25-triol
VVD0038
Sachiko Yamada
(17Z)-1a,25-(OH)2-17,20-didehydro-21-nor-D3
C26H40O3 400.594 Download ChemDraw structure file






From 4-hydroxyhydrindanone via introduction of the side chain and A-ring fragments. (Ref. 0315)



37
(24R,25S)-25,26-epoxy-1a,24-dihydroxy-27-norvitamin D3 / (24R,25S)-25,26-epoxy-1a,24-dihydroxy-27-norcholecalciferol
(5Z,7E)-(1S,3R,24R,25S)-25,26-epoxy-27-nor-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0039
Sachiko Yamada
25S,26-epoxy-1a,24R-(OH)2-27-nor-D3
C26H40O4 416.593 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for pig intestinal receptor and human vitamin D binding protein: 3% and 21%, respectively. Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60) and osteosarcoma (MG-63) cells: both < 1%. Elevation of serum calcium, serum osteocalcin, bone calcium and duodenal calbindin in rachitic chicks: all < 1%. (Ref. 0240)





By Sharpless kinetic epoxidation of the corresponding olefinic precursor. (Ref. 0243)



38
(24S,25R)-25,26-epoxy-1a,24-dihydroxy-27-norvitamin D3 / (24S,25R)-25,26-epoxy-1a,24-dihydroxy-27-norcholecalciferol
(5Z,7E)-(1S,3R,24S,25R)-25,26-epoxy-27-nor-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0040
Sachiko Yamada
25R,26-epoxy-1a,24S-(OH)2-27-nor-D3
C26H40O4 416.593 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for pig intestinal receptor and human vitamin D binding protein : 2% and 5%, respectively. Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60) and osteosarcoma (MG-63) cells : both < 1%. Elevation of serum calcium, serum osteocalcin, bone calcium, and duodenal calbindin in rachitic chicks: all < 1%. (Ref. 0240)





By Sharpless kinetic epoxidation of the corresponding olefinic precursor. (Ref. 0243)



39
1a,25-dihydroxy-24-oxo-22-oxavitamin D3 / 1a,25-dihydroxy-24-oxo-22-oxacholecalciferol
(5Z,7E)-(1S,3R)-1,3,25-trihydroxy-22-oxa-9,10-seco-5,7,10(19)-cholestatrien-24-one
VVD0041
Sachiko Yamada
1a,25-(OH)2-24-oxo-22-oxa-D3
C26H40O5 432.593 Download ChemDraw structure file
Antiproliferative activity (HL-60) was the same as that of 22-oxacalcitriol (OCT). The binding affinity for bovine thymus vitamin D receptor was 1/2 of OCT. (Ref. 0213)
lmax (EtOH) (nm) 263, lmin (nm) 227 (Ref. 0213)
1H-NMR (d, CDCl3) 0.53 (3H, s), 1.21 (3H, d, J = 6.3 Hz), 1.40 (6H, s), 4.18-4.27 (1H, m), 4.22 and 4.43 (each 1H, d, J = 16.3 Hz), 4.39-4.48 (1H, m), 5.00 (1H, s), 5.33 (1H, s), 6.03 (1H, d, J = 12.0 Hz), 6.37 (1H, d, J = 12.0 Hz) (Ref. 0213)
m/z 432 (M+), 59 (100%) (Ref. 0213)
Colorless oil. (Ref. 0213)
Preparative TLC developed with AcOEt. (Ref. 0213)

Synthesis from dehydroepiandrostertone via the 5,7-diene by photochemical method. (Ref. 0213)



40
25-hydroxy-3-deoxy-2-oxavitamin D3 / 25-hydroxy-3-deoxy-2-oxacholecalciferol
(5Z,7E)-2-oxa-9,10-seco-5,7,10(19)-cholestatrien-25-ol
VVD0042
Sachiko Yamada
3-deoxy-25-OH-2-oxa-D3
C26H42O2 386.610 Download ChemDraw structure file






From 25,26-dehydro-8-enol triflate upper half and ring A precursor, 2-methyll-3-ethynyl-2,3-dehydro-d-butyrolactone. Coupling of the two precursors followed by catalytic partial hydrogenation and DIBAL reduction afforded 1,3-dihydroxy-2-nor-1,2-seco-vitamin D after spontaneous 1,7-hydrogen shift which by A ring cyclization and oxymercuration-demercuration (25-hydroxy introduction) afforded the title compound. (Ref. 0330)



41
1a,25-dihydroxy-3-deoxy-3-thiavitamin D3 / 1a,25-dihydroxy-3-deoxy-3-thiacholecalciferol
(5Z,7E)-(1R)-9,10-seco-3-thia-5,7,10(19)-cholestatriene-1,25-diol
VVD0043
Sachiko Yamada
3-deoxy-3-thia-1a,25-(OH)2D3
C26H42O2S 418.676 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect): Intestinal calcium absorption and bone calcium mobilization in vitamin D deficient, rachitic chicks : 20% and <10%, respectively. Ability to bind to chick intestinal receptor: 14.5%. (Ref. 0281)
1H-NMR (d) 0.53 (3H, s, 18C-CH3), 0.93 (3H, d, J = 6.3 Hz, 21C-CH3), 1.22 (6H, s, 26- and 27-C-2CH3), 2.75-2.85 (2H, m, 2- and 9b-H), 3.06 (1H, dd, J = 13.4 and 2.3 Hz, 2-H,), 3.12 and 3.33 (2H, AB pattern, J = 12.9 Hz, 2times4-H), 4.36 (1H, m, 1-H), 4.90 (1H, s, 19-H), 5.29 (1H, s, 19-H), 5.93 and 6.43 (2H, AB pattern, J = 11.2 Hz, 6- and 7-H) (Ref. 0281)




Synthesis of the title compound and its 1b-epimer was achieved starting from CD-fragment and enantiomerically pure A-ring fragments, trimethylsilylenynes, which were prepared from 4-methylthiacyclohexane-3,5-dione. (Ref. 0281)



42
1b,25-dihydroxy-3-deoxy-3-thiavitamin D3 / 1b,25-dihydroxy-3-deoxy-3-thiacholecalciferol
(5Z,7E)-(1S)-9,10-seco-3-thia-5,7,10(19)-cholestatriene-1,25-diol
VVD0044
Sachiko Yamada
3-deoxy-3-thia-1b,25-(OH)2D3
C26H42O2S 418.676 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Intestinal calcium absorption and bone calcium mobilization in vitamin D deficient, rachitic chicks: <20% and <10%, respectively. Ability to bind to chick intestinal receptor : 1.23%. (Ref. 0281)
1H-NMR (d) 0.53 (3H, s, 18C-CH3), 0.93 (3H, d, J = 6.0 Hz, 21C-CH3), 1.22 (6H, s, 26-, 27-C-2CH3), 2.65-2.90 (3H, m, 2- and 9b-H), 3.08 (1H, dd, J = 13.2 and 2.1 Hz, 2-H), 3.10 and 3.35 (2H, two d, AB pattern, J = 12.9 Hz, 2times4-H), 4.36 (1H, m, 1-H), 4.91 (1H, br s, 19-H), 5.30 (1H, br s, 19-H), 5.96 and 6.43 (2H, two d, AB pattern, J = 11.2 Hz, 6-, 7-H) (Ref. 0281)




Synthesis of the title compound and its 1a-epimer was achieved starting from CD-fragment and enantiomerically pure A-ring fragments, trimethylsilylenynes, which were prepared from 4-methylthiacyclohexane-3,5-dione. (Ref. 0281)



43
(5Z)-1,25-dihydroxy-3-thiavitamin D3 / (5Z)-1,25-dihydroxy-3-thiacholecalciferol
(5Z,7E)-(1R)-9,10-seco-3-thia-5,7,10(19)-cholestatriene-1,25-diol
VVD0045
Sachiko Yamada
(5Z)-3-thia-1,25-(OH)2D3
C26H42O2S 418.676 Download ChemDraw structure file
Affinity for chicken intestinal recepto : 0.1% of 1,25-(OH)2D3 effect. Inhibitory effect of a series of 3-thiavitamin D derivatives on 25-OHD3 1a-hydroxylase was evaluated. (Ref. 0306)
(100% EtOH) lmax (nm) (emax) 268 (18300) (Ref. 0306)
1H-NMR (d, CDCl3, 300MHz) 0.56 (3H, s, 18C-CH3), 0.94 (3H, d, J = 6.3 Hz, 21C-CH3), 1.22 (6H, s, 26C- and 27C-CH3), 2.75-2.90 (2H, m, 2- and 9b-H), 3.08 (1H, dd, J = 13.2, 2.3 Hz, 2-H), 3.25 and 3.44 (2H, AB pattern, J = 13.5 Hz, 4-H2), 4.39 (1H, m, 1-H), 4.99 (1H, s, 19-H), 5.01 (1H, distorted d, J = 1.8 Hz, 19-H), 5.79 and 6.41 (2H, AB pattern, J = 11.5 Hz, 6- and 7-H) (Ref. 0306)
m/z 418 (34, M+), 400 (7, M+-H2O), 385 (20), 372 (10), 354 (5), 342 (2), 318 (4), 289 (7), 271 (15), 246 (14), 213 (7), 189 (9), 175 (14), 154 (base, A-ring portion due to C7- and C8-cleavage), 135 (68), 121 (12), 108 (66), 95 (31), 81 (22), 69 (13), 59 (16) (Ref. 0306)



From corresponding 5E-vitamin D (1a,25-dihydroxy-3-deoxy-3-thiavitamin D3) by iodine catalyzed isomerization followed by HPLC separation. (Ref. 0306)



44
1a-hydroxy-22-oxavitamin D3 / 1a-hydroxy-22-oxacholecalciferol
(5Z,7E)-(1S,3R)-22-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0046
Sachiko Yamada
1a-OH-22-oxa-D3
C26H42O3 402.610 Download ChemDraw structure file

[a]d-24 -30.2 deg (c = 0.86 in EtOH) (Ref. 0208)
lmax (EtOH) (nm) 262 (Ref. 0208)
1H-NMR (d, CDCl3) 0.53 (3H, s), 0.89 (3H, d, J = 6.7 Hz), 0.90 (3H, d, J = 6.7 Hz), 1.16 (3H, d, J = 6.2 Hz), 2.32 (1H, dd, J = 13.6 and 6.8 Hz), 2.60 (1H, dd, J = 13.6 and 3.4 Hz), 2.84 (1H, dd, J = 12.2 and 3.4 Hz), 3.10-3.30 (2H, m), 3.48-3.62 (1H, m), 4.14-4.28 (1H, m), 4.38-4.50 (1H, m), 4.99 (1H, t, J = 1.6 Hz), 5.32 (1H, t, J = 1.6 Hz), 6.02 (1H, d, J = 11.4 Hz), 6.37 (1H, d, J = 11.4 Hz) (Ref. 0208)
m/z 402 (M+), 71 (100%) (Ref. 0208)
Colorless glass (Ref. 0208)


Synthesis from dehydroepiandrostertone via 5,7-diene compound by photochemical method. (Ref. 0208)



45
25-hydroxy-23-oxavitamin D3 / 25-hydroxy-23-oxacholecalciferol
(5Z,7E)-(3S)-23-oxa-9,10-seco-5,7,10(19)-cholestatriene-3,25-diol
VVD0047
Sachiko Yamada
25-OH-23-oxa-D3
C26H42O3 402.610 Download ChemDraw structure file
Affinity for chick intestinal receptor: 6% of 1,25-(OH)2D3. (Ref. 0359)









46
1a,25-dihydroxy-24-norvitamin D3 / 1a,25-dihydroxy-24-norcholecalciferol
(5Z,7E)-(1S,3R)-24-nor-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0048
Sachiko Yamada
1a,25-(OH)2-24-nor-D3
C26H42O3 402.610 Download ChemDraw structure file
HL-60 human promyelocytes differentiation: ED50 in nitro blue tetrazolium reduction, phagocytic activity and nonspecific acid esterase activity are 1.5 times 10-7 M, 1.2 times 10-7 M and 1.6 times 10-7 M, respectively, when 1,25-(OH)2D3 shows the respective ED50 values of 1.0 times 10-8 M, 1.0 times 10-8 M and 1.1 times 10-8 M, respectively. (Ref. 0228)
Biological activity (% of 1,25-(OH)2D3effect) : Intestinal calcium absorption in chick, 2.0% ; Bone calcium mobilization in chick, 2.0% ; Competitive binding to the vitamin D receptor in chick intetine, 1.0% ; Inhibition of clonal growth of human leukemia cells (HL-60), ED50 was not reached. (Ref. 0238)









47
1a,25-dihydroxy-19-norprevitamin D3 / 1a,25-dihydroxy-19-norprecholecalciferol
(6Z)-(1S,3R)-19-nor-9,10-seco-5(10),6,8-cholestatriene-1,3,25-triol
VVD0049
Sachiko Yamada
1a,25-(OH)2-19-norpre-D3
C26H42O3 402.610 Download ChemDraw structure file
Biological activity : The affinity of the title compound for the intestinal vitamin D receptor and plasma vitamin D binding protein was 1 and 6% of that of 1,25-(OH)2D3, respectively. The in vitro effects on human promyeloid leukemia (HL-60 cell) differentiation and osteocalcin secretion by human osteosarcoma (MG-63) cells by the title compound were poor (2%). This compound showed no in vivo calcemic effects. (Ref. 0222)





Lower-half of the vitamin, silyl protected 1-ethynyl-1-cyclohexene-3S,5R-diol, was synthesized from shikimic acid in 8 steps in 25% overall yield. Palladium catalyzed coupling of the lower-half with upper-half (25-hydroxy-des-AB-cholest-8-en-8-yl triflate) yielded 6,7-didehydroprevitamin D which by partial hydrogenation followed by deprotection afforded the target vitamin, 1,25-(OH)2-19-norpre-D3. (Ref. 0230)



48
1a,25-dihydroxy-21-norvitamin D3 / 1a,25-dihydroxy-21-norcholecalciferol
(5Z,7E)-(1S,3R)-21-nor-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0050
Sachiko Yamada
1a,25-(OH)2-21-nor-D3
C26H42O3 402.610 Download ChemDraw structure file
Differentiation inducing activity of HL-60 (ED50):2.9 times 10-8 M (1,25-(OH)2D3: 8.3 times 10-9 M). Binding affinity for chick intestinal receptor: 1/10 of 1a,25-(OH)2D3. Calcemic activity at the dose of 500 mg/kg in normal mice ; 9.68 pm 0.15 (1.25-(OH)2D3 ; 11.04 pm 0.12 at 10mg/kg). (Ref. 0209)
lmax (EtOH) (nm) 262, lmin (nm) 227 (Ref. 0209)
(neat) 3380, 1470, 1450, 1375, 1060 cm-1 (Ref. 0209)
1H-NMR (d) 0.44 (3H, s), 1.21 (6H, s), 1.25 (3H, br s), 4.14-4.28 (1H, br), 4.34-4.47 (1H, br), 5.00 (1H, s), 5.33 (1H, s), 6.01 (1H, d, J = 11.0 Hz), 6.38 (1H, d, J = 11.0 Hz) (Ref. 0209)
m/z 402 (M+), 134 (100%) (Ref. 0209)

Preparative TLC devbeloped twice with CH2Cl2-EtOH (50 : 7) (Ref. 0209)

Synthesis from dehydroepiandrostertone via 5,7-diene compound by photochemical method. (Ref. 0209)



49
1a,25-dihydroxy-3-deoxy-3-thiavitamin D3 3-oxide / 1a,25-dihydroxy-3-deoxy-3-thiacholecalciferol 3-oxide
(5E,7E)-(1R,3R)-1,25-dihydroxy-9,10-seco-3-thia-5,7,10(19)-cholestatriene 3-oxide
VVD0051
Sachiko Yamada
3-deoxy-3-thia-1a,25-(OH)2 3-oxide
C26H42O3S 434.676 Download ChemDraw structure file
Affinity for chicken intestinal receptor : 27.0% of 1,25-(OH)2D3 effect. Inhibitory effect on 25-OHD3 1a-hydroxylase activity was evaluated. (Ref. 0306)
lmax (100% EtOH) (nm) (e) 268 (17500) (Ref. 0306)
1H-NMR (d, CDCl3, 300MHz) 0.53 (3H, s, 18C-CH3), 0.94 (3H, d, J = 6.0 Hz, 21C-CH3), 1.22 (6H, s, 26C- and 27C-CH3), 2.80 (1H, br d, J = 11.7 Hz, 9b-H), 3.00 (1H, dd, J = 12.8, 9.2 Hz, 2-H), 3.20 (1H, d with fine structure, J = 12.8 Hz, 2-H), 3.55 and 3.65 (2H, AB pattern, J = 13.0 Hz, 4-H2), 4.81 (1H, m, 1-H), 5.14 (1H, s, 19-H), 5.49 (1H, s, 19-H), 5.97 and 6.57 (2H, AB pattern, J = 11.1 Hz, 6- and 7-H) (Ref. 0306)
m/z 434 (3, M+), 416 (13, M+-H2O), 399 (7), 381 (5), 367 (9), 350 (11), 323 (6), 305 (3), 287 (5), 239 (8), 225 (5), 213 (7), 197 (7), 185 (9), 171 (10), 159 (15), 145 (22), 133 (21), 119 (30), 107 (28), 95 (40), 81 (42), 69 (58), 59 (base) (Ref. 0306)



From corresponding 3-thiavitamin D (1a,25-dihydroxy-3-deoxy-3-thiavitamin D3) by oxidation with mCPBA followed by separation of epimers at S-3 by HPLC. (Ref. 0306)



50
(5E)-(3S)-1a,25-dihydroxy-3-deoxy-3-thiavitamin D3 3-oxide / (5E)-(3S)-1a,25-dihydroxy-3-deoxy-3-thiacholecalciferol 3-oxide
(5E,7E)-(1R,3S)-1,25-dihydroxy-9,10-seco-3-thia-5,7,10(19)-cholestatrien 3-oxide
VVD0052
Sachiko Yamada
(5E)-3-deoxy-3S-thia-1a,25-(OH)2D3 3-oxide
C26H42O3S 434.676 Download ChemDraw structure file
Affinity for chicken intestinal receptor : 0.8% of 1,25-(OH)2D3 effect. Inhibitory effect on 25-OHD3 1a-hydroxylase activity was evaluated. (Ref. 0306)
lmax (100% EtOH) (nm) (e) 272 (18000) (Ref. 0306)
1H-NMR (d, CDCl3, 300MHz) 0.53 (3H, s, 18C-CH3), 0.93 (3H, d, J = 6.3 Hz, 21C-CH3), 1.21 (6H, s, 26C- and 27C-CH3), 2.76 (1H, dd, J = 14.0, 2.0 Hz, 2-H), 2.85 (1H, br d, J = 13.5 Hz, 9b-H), 3.47 (1H, ddd, J = 14.0, 3.0 Hz, 2-H), 3.60 and 3.80 (2H, AB pattern, J = 13.2 Hz, 4-H2 ; the 3.80 signal was further split, d, J = 2.7 Hz), 4.62 (1H, m, 1-H), 5.08 (1H, d, J = 1.8 Hz, 19-H), 5.37 (1H, d, J = 1.8 Hz, 19-H), 6.05 and 6.72 (2H, AB pattern, J = 11.1 Hz, 6- and 7-H) (Ref. 0306)
m/z 434 (25, M+), 416 (52, M+-H2O), 398 (50), 383 (24), 367 (31), 341 (93), 325 (77), 309 (25), 287 (23), 269 (28), 239 (27), 213 (58), 185 (55), 171 (68), 145 (62), 119 (base), 105 (30), 95 (57), 81 (53), 69 (78), 59 (56) (Ref. 0306)



From corresponding 3-thiavitamin D (1a,25-dihydroxy-3-deoxy-3-thiavitamin D3) by mCPBA oxidation followed by HPLC separation from 3-epimer. (Ref. 0306)



51
(5Z)-1a,25-dihydroxy-3-deoxy-3-thiavitamin D3 3-oxide / (5Z)-1a,25-dihydroxy-3-deoxy-3-thiacholecalciferol 3-oxide
(5Z,7E)-(1R,3R)-1,25-dihydroxy-9,10-seco-3-thia-5,7,10(19)-cholestatriene 3-oxide
VVD0053
Sachiko Yamada
(5Z)-3-deoxy-3-thia-1a,25-(OH)2D3 3-oxide
C26H42O3S 434.676 Download ChemDraw structure file
Affinity for chicken intestinal receptor : 3.7% of 1,25-(OH)2D3 effect. Inhibitory effect on 25-OHD3 1a-hydroxylase activity was evaluated. (Ref. 0306)
lmax (100% EtOH) (nm) (e) 272 (18000) (Ref. 0306)
1H-NMR (d, CDCl3, 300MHz) 0.56 (3H, s, 18C-CH3), 0.94 (3H, d, J = 6.3 Hz, 21C-CH3), 1.22 (6H, s, 26C- and 27C- CH3), 2.85 (1H, br d, J = 12.6 Hz, 9b-H), 3.10 (1H, dd, J = 12.8, 3.0 Hz, 2-H), 3.30 (1H, ddd, J = 12.8, 7.3, 1.3 Hz, 2-H), 3.63 and 4.03 (2H, AB pattern, J = 13.1 Hz, 4-H2), 4.88 (1H, m, 1-H), 5.16 (1H, br s, 19-H), 5.26 (1H, br s, 19-H), 5.86 and 6.78 (2H, AB pattern, J = 11.5 Hz, 6- and 7-H) (Ref. 0306)
m/z 434 (19, M+), 416 (48, M+-H2O), 399 (21), 367 (25), 350 (55), 335 (11), 287 (19), 267 (13), 239 (32), 185 (26), 145 (63), 107 (83), 95 (base), 81 (97), 69 (11), 59 (16) (Ref. 0306)



From corresponding (5E)-vitamin D (1a,25-dihydroxy-3-deoxy-3-thiavitamin D3 3-oxide) by geometrical isomerization catalyzed by iodine. (Ref. 0306)



52
(5Z)-(3S)-1a,25-dihydroxy-3-deoxy-3-thiavitamin D3 3-oxide / (5Z)-(3S)-1a,25-dihydroxy-3-deoxy-3-thiacholecalciferol 3-oxide
(5Z,7E)-(1R,3S)-1,25-dihydroxy-9,10-seco-3-thia-5,7,10(19)-cholestatrien 3-oxide
VVD0054
Sachiko Yamada
(5Z)-3-deoxy-3S-thia-1a,25-(OH)2D3 3-oxide
C26H42O3S 434.676 Download ChemDraw structure file
Affinity for chicken intestinal receptor : 0.9% of 1,25-(OH)2D3 effect. Inhibitory effect on 25-OHD3 1a-hydroxylase activity was evaluated. (Ref. 0306)
lmax (100% EtOH) (nm) (e) 270 (17800) (Ref. 0306)
1H-NMR (d, CDCl3, 300MHz) 0.57 (3H, s, 18C-CH3), 0.94 (3H, d, J = 6.0 Hz, 21C-CH3), 1.22 (6H, s, 26C- and 27C-CH3), 2.77 (1H, dd, J = 13.9, 2.8 Hz, 2-H), 2.85 (1H, br d, J = 12.6 Hz, 9b-H), 3.40 (1H, d, J = 14.0 Hz, 4-H), 3.50 (1H, ddd, J = 13.9, 4.2, 2.6 Hz, 2-H), 4.30 (1H, dd, J = 14.0, 2.3 Hz, 4-H), 4.64 (1H, m, 1-H), 4.80 (1H, d, J = 10.2 Hz ; this has been assigned to the OH), 5.10 (1H, s, 19-H), 5.21 (1H, d, J = 1.2 Hz, 19-H), 5.86 and 6.96 (2H, AB pattern, J = 11.4 Hz, 6- and 7-H) (Ref. 0306)
m/z 434 (5, M+), 416 (11, M+-H2O), 399 (5), 367 (9), 350 (14), 335 (4), 287 (6), 267 (5), 239 (8), 211 (6), 185 (9), 133 (25), 105 (32), 95 (46), 81 (49), 69 (64), 59 (base) (Ref. 0306)



From corresponding 3-thiavitamin D (1a,25-dihydroxy-3-deoxy-3-thiavitamin D3) by mCPBA oxidation followed by iodine catalyzed isomerization. (Ref. 0306)



53
1a,25-dihydroxy-22-thiavitamin D3 / 1a,25-dihydroxy-22-thiacholecalciferol
(5Z,7E)-(1S,3R)-9,10-seco-22-thia-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0055
Sachiko Yamada
22-thia-1a,25-(OH)2D3
C26H42O3S 434.676 Download ChemDraw structure file

lmax (EtOH) (nm) 264, lmin (nm) 227 (Ref. 0215)
(neat) 3380, 2920, 1440, 1370, 1050 cm-1 (Ref. 0215)
1H-NMR (d, CDCl3, 200MHz) 0.58 (3H, s), 1.25 (6H, s), 1.39 (3H, d, J = 6.6 Hz), 2.63 (2H, t, J = 7.8 Hz), 4.17-4.30 (1H, br), 4.35-4.48 (1H, br), 5.00 (1H, s), 5.33 (1H, s), 6.01 (1H, d, J = 11.1 Hz), 6.37 (1H, d, J = 11.1 Hz) (Ref. 0215)

HRMS Calcd 434.2855, Found 434.2829 (Ref. 0215)


Synthesis from dehydroepiandrostertone via the 5,7-diene by photochemical method. (Ref. 0215)



54
1a,25-dihydroxy-22-thia-20-epivitamin D3 / 1a,25-dihydroxy-22-thia-20-epicholecalciferol
(5Z,7E)-(1S,3R,20R)-9,10-seco-22-thia-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0056
Sachiko Yamada
22-thia-1a,25-(OH)2-20-epi-D3
C26H42O3S 434.676 Download ChemDraw structure file

lmax (EtOH) (nm) 264, lmin (nm) 227 (Ref. 0215)
(neat) 3390, 2920, 1450, 1380, 1060 cm-1 (Ref. 0215)
1H-NMR (d, CDCl3, 200MHz) 0.62 (3H, s), 1.25 (6H, s), 1.30 (3H, d, J = 6.6 Hz), 2.61 (2H, t, J = 8.3 Hz), 4.13-4.30 (1H, br), 4.36-4.48 (1H, br), 5.00 (1H, s), 5.33 (1H, s), 6.02 (1H, d, J = 11.1 Hz), 6.37 (1H, d, J = 11.1 Hz) (Ref. 0215)

HRMS Calcd 434.2855, Found 434.2837 (Ref. 0215)


Synthesis from dehydroepiandrostertone via the 5,7-diene by photochemical method. (Ref. 0215)



55
1a,25-dihydroxy-23-thiavitamin D3 / 1a,25-dihydroxy-23-thiacholecalciferol
(5Z,7E)-(1S,3R)-9,10-seco-23-thia-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0057
Sachiko Yamada
23-thia-1a,25-(OH)2D3
C26H42O3S 434.676 Download ChemDraw structure file
Differentiation inducing activity of HL-60 was shown in comparison with 1,25-(OH)2D3. (Ref. 0210)
lmax (EtOH) (nm) 263, lmin (nm) 227 (Ref. 0210)
1H-NMR (d, CDCl3) 0.56 (3H, s), 1.10 (3H, d, J = 6.2 Hz), 1.28 (6H, s), 2.53-2.89 (2H, m), 2.63 (2H, s), 4.09-4.29 (1H, br), 4.36-4.49 (1H, br), 4.99 (1H, s), 5.32 (1H, s), 6.01 (1H, d, J = 11.4 Hz), 6.37 (1H, d, J = 11.4 Hz) (Ref. 0210)
m/z 434 (M+), 134 (100%) (Ref. 0210)

1)flash column chromatography using CH2Cl2-EtOH (5 : 0.3), 2)Preparative TLC developed twice with CH2Cl2-EtOH (10 : 1) (Ref. 0210)

Synthesis from dehydroepiandrostertone via 5,7-diene compound by photochemical method. (Ref. 0210)



56
(24R)-1a,24-dihydroxy-22-oxavitamin D3 / (24R)-1a,24-dihydroxy-22-oxacholecalciferol
(5Z,7E)-(1S,3R,24R)-22-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0058
Sachiko Yamada
1a,24R-(OH)2-22-oxa-D3
C26H42O4 418.609 Download ChemDraw structure file
The activity to induce differentiation of human myeloid leukemia cells (HL-60) into macrophases in vitro estimated by superoxide anion generation : ED50 = 9.17 times 10-9 M [ED50 of 1,25-(OH)2D3 : 3.76 times 10-9 M, ED50 of OCT : 1.16 times 10-9 M] the binding affinity for the chick embryonic intestinal 1,25-(OH)2D3 receptor : 0.016, 1,25-(OH)2D3 : 1, OCT : 0.17 (Ref. 0206)
[a]d-24 46.00 deg (c = 0.1 in EtOH) (Ref. 0206)
lmax (EtOH) (nm) 263, lmin (nm) 227 (Ref. 0206)
(neat) 3390, 1470, 1450, 1375, 1055 cm-1 (Ref. 0206)
1H-NMR (d, CDCl3) 0.53 (3H, s), 0.90 (3H, d, J = 6.8 Hz), 0.97 (3H, d, J = 6.8 Hz), 1.18 (3H, d, J = 6.0 Hz), 3.08 (1H, t, J = 8.8 Hz), 3.20-3.32 (1H, m), 3.36-3.48 (1H, m), 3.67 (1H, dd, J = 3.0 and 9.1 Hz), 4.17-4.28 (1H, br), 4.37-4.48 (1H, br), 4.99 (1H, s), 5.33 (1H, s), 6.02 (1H, d, J = 11.4 Hz), 6.37 (1H, d, J = 11.4 Hz) (Ref. 0206)
m/z 418 (M+), 87 (100%) (Ref. 0206)
HRMS Calcd 418.3083, Found 418.3080 (Ref. 0206)


Synthesis from dehydroepiandrostertone via 1a,3b-dihydroxy-20(S)-[2(R)-hydroxy-3-methylbutyloxy]pregna-5,7-diene by photochemical method. (Ref. 0206)



57
(24R)-1a,24-dihydroxy-22-oxa-20-epivitamin D3 / (24R)-1a,24-dihydroxy-22-oxa-20-epicholecalciferol
(5Z,7E)-(1S,3R,20R,24R)-22-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0059
Sachiko Yamada
1a,24R-(OH)2-20-epi-22-oxa-D3
C26H42O4 418.609 Download ChemDraw structure file
The activity to induce differentiation of human myeloid leukemia cells (HL-60) into macrophases in vitro estimated by superoxide anion generation : ED50 = 2.40 times 10-8 M [ED50 of 1,25-(OH)2D3 : 3.76 times 10-9 M, ED50 of OCT : 1.16 times 10-9 M] the binding affinity for the chick embryonic intestinal 1,25-(OH)2D3 receptor : 0.16, 1,25-(OH)2D3 : 1, OCT : 0.17 (Ref. 0206)
[a]d-23 -30.68 deg (c = 0.365 in EtOH) (Ref. 0206)
(EtOH) lmax (nm) 263, lmin (nm) 227 (Ref. 0206)
(neat) 3400, 1450, 1370, 1110, 1060 cm-1 (Ref. 0206)
1H-NMR (d, CDCl3) 0.57 (3H, s), 0.91 (3H, d, J = 6.8 Hz), 0.98 (3H, d, J = 6.8 Hz), 1.10 (3H, d, J = 6.2 Hz), 3.23-3.40 (2H, m), 3.40-3.53 (2H, m), 4.16-4.28 (1H, br), 4.37-4.48 (1H, br), 4.99 (1H, s), 5.31 (1H, s), 5.99 (1H, d, J = 11.4 Hz), 6.38 (1H, d, J = 11.4 Hz) (Ref. 0206)
m/z 418 (M+), 87 (100%) (Ref. 0206)
HRMS Calcd 418.3083, Found 418.3080 (Ref. 0206)


Synthesis from dehydroepiandrostertone via 1a,3b-dihydroxy-20(R)-[2(R)-hydroxy-3-methylbutyloxy]pregna-5,7-diene by photochemical method. (Ref. 0206)



58
(24S)-1a,24-dihydroxy-22-oxavitamin D3 / (24S)-1a,24-dihydroxy-22-oxacholecalciferol
(5Z,7E)-(1S,3R,24S)-22-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0060
Sachiko Yamada
1a,24S-(OH)2-22-oxa-D3
C26H42O4 418.609 Download ChemDraw structure file
The activity to induce differentiation of human myeloid leukemia cells (HL-60) into macrophases in vitro estimated by superoxide anion generation: ED50 = 1.37 times 10-9 M [ED50 of 1,25-(OH)2D3 : 3.76 times 10-9 M, ED50 of OCT : 1.16 times 10-9 M] the binding affinity for the chick embryonic intestinal 1,25-(OH)2D3 receptor : 0.34, 1,25-(OH)2D3 : 1, OCT : 0.17. (Ref. 0206)
[a]d-24 56.0 deg (c = 0.1 in EtOH) (Ref. 0206)
(EtOH) lmax (nm) 263, lmin (nm) 227 (Ref. 0206)
(neat) 3390, 1470, 1450, 1370, 1050 cm-1 (Ref. 0206)
1H-NMR (d, CDCl3) 0.53 (3H, s), 0.90 (3H, d, J = 6.8 Hz), 0.97 (3H, d, J = 6.6 Hz), 1.17 (3H, d, J = 6.2 Hz), 3.22-3.36 (2H, m), 3.36-3.49 (2H, m), 4.16-4.28 (1H, br), 4.37-4.48 (1H, br), 5.00 (1H, s), 5.34 (1H, s), 6.02 (1H, d, J = 11.4 Hz), 6.37 (1H, d, J = 11.4 Hz) (Ref. 0206)
m/z 418 (M+), 87 (100%) (Ref. 0206)
HRMS Calcd 418.3083, Found 418.3078 (Ref. 0206)


Synthesis from dehydroepiandrostertone via 1a,3b-dihydroxy-20(S)-[2(S)-hydroxy-3-methylbutyloxy]pregna-5,7-diene by photochemical method. (Ref. 0206)



59
(24S)-1a,24-dihydroxy-22-oxa-20-epivitamin D3 / (24S)-1a,24-dihydroxy-22-oxa-20-epicholecalciferol
(5Z,7E)-(1S,3R,20R,24S)-22-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0061
Sachiko Yamada
1a,24S-(OH)2-20-epi-22-oxa-D3
C26H42O4 418.609 Download ChemDraw structure file
The activity to induce differentiation of human myeloid leukemia cells (HL-60) into macrophases in vitro estimated by superoxide anion generation : ED50 = 4.68 times 10-8 M [ED50 of 1,25-(OH)2D3 : 3.76 times 10-9 M, ED50 of OCT : 1.16 times 10-9 M] the binding affinity for the chick embryonic intestinal 1,25-(OH)2D3 receptor : 0.003, 1,25-(OH)2D3 : 1, OCT : 0.17 (Ref. 0206)
[a]d-23 -24.24 deg (c = 0.165 in EtOH) (Ref. 0206)
(EtOH) lmax (nm) 263, lmin (nm) 227 (Ref. 0206)
(neat) 3390, 1450, 1370, 1055 cm-1 (Ref. 0206)
1H-NMR (d, CDCl3) 0.57 (3H, s), 0.90 (3H, d, J = 6.8 Hz), 0.97 (3H, d, J = 6.8 Hz), 1.10 (3H, d, J = 6.2 Hz), 3.10 (1H, t, J = 8.6 Hz), 3.24-3.35 (1H, m), 3.35-3.48 (1H, m), 3.61 (1H, dd, J = 3.0 and 9.1 Hz), 4.15-4.27 (1H, br), 4.26-4.34 (1H, br), 4.97 (1H, s), 5.30 (1H, s), 5.97 (1H, d, J = 11.4 Hz), 6.36 (1H, d, J = 11.4 Hz) (Ref. 0206)
m/z 418 (M+), 87 (100%) (Ref. 0206)
HRMS Calcd 418.3083, Found 418.3124 (Ref. 0206)


Synthesis from dehydroepiandrostertone via 1a,3b-dihydroxy-20(R)-[2(S)-hydroxy-3-methylbutyloxy]pregna-5,7-diene by photochemical method. (Ref. 0206)



60
1a,25-dihydroxy-22-oxavitamin D3 / 1a,25-dihydroxy-22-oxacholecalciferol
(5Z,7E)-(1S,3R)-22-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0062
Sachiko Yamada
1a,25-(OH)2-22-oxa-D3
C26H42O4 418.609 Download ChemDraw structure file
The activity inducing differentiation of human myeloid leukemia cells (HL-60) into macrophases in vitro estimated by superoxide anion generation : ED50 of OCT : 4.90 times 10-9 M, ED50 of 1,25(OH)2D3 : 1.70 times 10-8 M. the binding affinity for the chick embryonic intestinal 1,25-(OH)2D3 receptor : 12.5%, 1,25-(OH)2D3 : 100%. (Ref. 0203)
(EtOH) lmax (nm) 262, lmin (nm) 227 (Ref. 0203)
(KBr) 3390, 1370, 1145, 1085, 1050 cm-1 (Ref. 0203)
1H-NMR (d, CDCl3) 0.54 (3H, s), 1.18 (3H, d, J = 6.3 Hz), 1.23 (6H, s), 2.31 (1H, dd, J = 13.7, 6.6 Hz), 2.60 (1H, dd, J = 13.7, 3.4 Hz), 2.82 (1H, dd, J = 12.0, 1.7 Hz), 3.25 (1H, quintet, J = 6.3 Hz), 3.47 (1H, dt, J = 9.1, 5.4 Hz), 3.75-3.91 (2H, m), 4.16-4.30 (1H, m), 4.36-4.50 (1H, m), 4.98 (1H, t, J = 1.4 Hz), 5.32 (1H, t, J = 1.4 Hz), 6.02 (1H, d, J = 11.4 Hz), 6.36 (1H, d, J = 11.4 Hz) (Ref. 0208)
m/z 418 (M+), 69 (100%) (Ref. 0208)
colorless glass (Ref. 0208)
1) Flash column chromatography with CH2Cl2/EtOH (12.5 : 1), 2) Flash column chromatography with AcOEt/n-hexane (6 : 1) (Ref. 0203)

Synthesis from dehydroepiandrostertone via 1a,3b-dihydroxy-20(S)-(3-hydroxy-3-methylbutyloxy)pregna-5,7-diene by photochemical method. (Ref. 0203)
Metabolism of the title compound was studied in four cultured cell models representing liver, keratinocyte and osteoblast, and 24-hydroxylated and 26-hydroxylated derivatives as well as the side-chain cleaved molecules, hexanor-1a,20-dihydroxyvitamin D3 and hexanor-20-oxo-1a-hydroxyvitamin D3 were identified. (Ref. 0323)


61
1a,25-dihydroxy-22-oxa-20-epivitamin D3 / 1a,25-dihydroxy-22-oxa-20-epicholecalciferol
(5Z,7E)-(1S,3R,20R)-22-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0063
Sachiko Yamada
1a,25-(OH)2-20-epi-22-oxa-D3
C26H42O4 418.609 Download ChemDraw structure file
The activity to induce differentiation of human myeloid leukemia cells (HL-60) into macrophases in vitro estimated by superoxide anion generation : ED50 = 1.46 times 10-9 M [ED50 of 1,25-(OH)2D3 : 3.76 times 10-9 M, ED50 of OCT: 1.16 times 10-9 M] the binding affinity for the chick embryonic intestinal 1,25-(OH)2D3 receptor : 0.08, 1,25-(OH)2D3 : 1, OCT : 0.17 (Ref. 0206)
[a]d-24 -66.0 deg (c = 0.1 in EtOH) (Ref. 0206)
(EtOH) lmax (nm) 263, lmin (nm) 227 (Ref. 0206)
(neat) 3390, 1455, 1370, 1060 cm-1 (Ref. 0206)
1H-NMR (d, CDCl3) 0.55 (3H, s), 1.13 (3H, d, J = 6.0 Hz), 1.23 (6H, s), 3.16-3.32 (1H, m), 3.36-3.58 (1H, m), 3.70-3.90 (1H, m), 4.13-4.27 (1H, m), 4.34-4.48 (1H, br), 4.99 (1H, s), 5.30 (1H, s), 5.99 (1H, d, J = 11.6 Hz), 6.38 (1H, d, J = 11.6 Hz) (Ref. 0206)
m/z 418 (M+), 69 (100%) (Ref. 0206)
HRMS Calcd 418.3083, Found 418.3058 (Ref. 0206)


Synthesis from dehydroepiandrostertone via 1a,3b-dihydroxy-20(R)-(3-hydroxy-3-methylbutyloxy)pregna-5,7-diene by photochemical method. (Ref. 0206)



62
1b,25-dihydroxy-22-oxavitamin D3 / 1b,25-dihydroxy-22-oxacholecalciferol
(5Z,7E)-(1R,3R)-22-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0064
Sachiko Yamada
1b,25-(OH)2-22-oxa-D3
C26H42O4 418.609 Download ChemDraw structure file
The antiproliferation activity on HL-60 was 0.003 [1.25-(OH)2D3 : 1]. The binding affinity for both vitamin D receptor and vitamin D binding protein was 0.7% of the effect of a,25-(OH)2D3. (Ref. 0214)
(EtOH) lmax (nm) 263, lmin (nm) 221 (Ref. 0214)
1H-NMR (d, CDCl3) 0.54 (3H, s), 1.19 (3H, d, J = 5.9 Hz), 1.24 (6H, s), 3.21-3.34 (1H, m), 3.43-3.55 (1H, m), 3.79-3.89 (1H, m), 4.05-4.15 (1H, m), 4.31-4.40 (1H, m), 5.00 (1H, s), 5.29 (1H, s), 6.06 (1H, d, J = 10.9 Hz), 6.44 (1H, d, J = 10.9 Hz) (Ref. 0214)
m/z 418 (M+), 69 (100%) (Ref. 0214)
HRMS Calcd 418.3083, Found 418.3112 (Ref. 0214)


Synthesis from OCT by inversion of the 1a-hydroxy group. (Ref. 0214)



63
1a,25-dihydroxy-23-oxavitamin D3 / 1a,25-dihydroxy-23-oxacholecalciferol
(5Z,7E)-(1S,3R)-23-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0065
Sachiko Yamada
1a,25-(OH)2-23-oxa-D3
C26H42O4 418.609 Download ChemDraw structure file
Activity of inducing HL-60 cell differentiation was compared with 1,25-(OH)2D3. (Ref. 0210)
lmax (EtOH) (nm) 263, lmin (nm) 227 (Ref. 0210)
1H-NMR (d, CDCl3) 0.57 (3H, s), 1.05 (3H, d, J = 6.2 Hz), 1.21 (6H, s), 3.11-3.47 (4H, m), 4.03-4.27 (1H, br), 4.35-4.47 (1H, br), 4.99 (1H, s), 5.35 (1H, s), 6.00 (1H, d, J = 11.4 Hz), 6.36 (1H, d, J = 11.4 Hz) (Ref. 0210)
m/z 418 (M+), 59 (100%) (Ref. 0210)

1)Flash column chromatography using CH2Cl2-EtOH (5 : 0.3), 2)Preparative TLC developed twice with CH2Cl2-EtOH (10 : 1) (Ref. 0210)

Synthesis from dehydroepiandrostertone via 5,7-diene compound by photochemical method.(Ref. 0210)



64
1a,25-dihydroxy-22-oxa-[2b-3H]vitamin D3 / 1a,25-dihydroxy-22-oxa-[2b-3H]cholecalciferol
(5Z,7E)-(1S,3R)-22-oxa-[2b-3H]-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0066
Sachiko Yamada
1a,25-(OH)2-22-oxa-[2b-3H]-D3
C26H413H1O4 793.563 Download ChemDraw structure file



15.0 Ci/mmol (Ref. 0218)


Synthesis by photochemical method from the [2b-3H]-5,7-diene. (Ref. 0218/0219)



65
1a,25-dihydroxy-20-oxa-[26,26,26-3H3]vitamin D3 / 1a,25-dihydroxy-20-oxa-[26,26,26-3H3]cholecalciferol
(5Z,7E)-(1S,3R)-22-oxa-[26,26,26-3H3]-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0067
Sachiko Yamada
1a,25-(OH)2-22-oxa-[26,26,26-3H3]-D3
C26H393H3O4 775.420 Download ChemDraw structure file



86.5 Ci/mmol (Ref. 0218)


Synthesis by photochemical method from the [26,26,26-3H3]-5,7-diene. (Ref. 0218)



66
(20S)-1a,20,25-trihydroxy-24-norvitamin D3/(20S)-1a,20,25-trihydroxy-24-norcholecalciferol
(5Z,7E)-(1S,3R,20S)-24-nor-9,10-seco-5,7,10(19)-cholestatriene-1,3,20,25-tetrol
VVD0068
Sachiko Yamada
1a,20S,25-(OH)3-24-nor-D3
C26H42O4 418.609 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of U 937 cell (human histiocytic lymphoma cell line) proliferation : <4% ; Binding for the 1,25-(OH)2D3 receptor from rachitic chicken intestine : <0.1% ; Calcemic activity : not determined. (Ref. 0279)





From (5E)-1a-hydroxy-20-keto-22,23,24,25,26,27-hexanorvitamin D3 derivative by addition of a Grignard reagent followed by photochemical isomerization and deprotection. (Ref. 0279)



67
(24R)-1a,24,25-trihydroxy-22-oxavitamin D3 / (24R)-1a,24,25-trihydroxy-22-oxacholecalciferol
(5Z,7E)-(1S,3R,24R)-22-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,24,25-tetrol
VVD0069
Sachiko Yamada
1a,24R,25-(OH)3-22-oxa-D3
C26H42O5 434.609 Download ChemDraw structure file
The antiproliferation activity towards HL-60 was 1/2 of 22-oxacalcitriol (OCT). The binding affinity for bovine thymus vitamin D receptor was 1/3 of OCT. (Ref. 0213)
[a]d-20 44.0 deg (c = 0.29 in EtOH) (Ref. 0212)
(EtOH) lmax (nm) 262, lmin (nm) 227 (Ref. 0212)
1H-NMR (d, CDCl3) 0.53 (3H, s), 1.19 (3H, d, J = 6.1 Hz), 1.22 (3H, s), 1.24 (3H, s), 3.26-3.32 (1H, m),3.37-3.47 (2H, m), 3.73-3.82 (1H, m), 4.16-4.27 (1H, m), 4.38-4.45 (1H, m), 4.99 (1H, s), 5.33 (1H, s), 6.02 (1H, d, J = 11.5 Hz), 6.37 (1H, d, J = 11.5 Hz) (Ref. 0212)
m/z 434 (M+), 134 (100%) (Ref. 0212)
Colorless foam. (Ref. 0213)
HRMS Calcd 434.3032, Found 434.3023 (Ref. 0212)
Preparative TLC developed twice with AcOEt. (Ref. 0213)

Synthesis from dehydroepiandrostertone via the 5,7-diene by photochemical method. (Ref. 0212/0213)



68
(24S)-1a,24,25-trihydroxy-22-oxavitamin D3 / (24S)-1a,24,25-trihydroxy-22-oxacholecalciferol
(5Z,7E)-(1S,3R,24S)-22-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,24,25-tetrol
VVD0070
Sachiko Yamada
1a,24S,25-(OH)3-22-oxa-D3
C26H42O5 434.609 Download ChemDraw structure file
The antiproliferation activity towards HL-60 was 1/3 of 22-oxacalcitriol (OCT). The binding affinity for bovine thymus vitamin D receptor was 1/22 of OCT. (Ref. 0213)
[a]d-20 29.0 deg (c = 0.19 in EtOH) (Ref. 0212)
(EtOH) lmax (nm) 263, lmin (nm) 227 (Ref. 0212)
1H-NMR (d, CDCl3) 0.54 (3H, s), 1.19 (3H, d, J = 5.8 Hz), 1.22 (3H, s), 1.25 (3H, s), 3.22-3.29 (1H, m),3.34-3.46 (2H, m), 3.76 (1H, br d, J = 6.3 Hz), 4.14-4.25 (1H, m), 4.37-4.44 (1H, m), 4.99 (1H, s), 5.33 (1H, s), 6.02 (1H, d, J = 11.0 Hz), 6.37 (1H, d, J = 11.0 Hz) (Ref. 0212)
m/z 434 (M+), 134 (100%) (Ref. 0212)
Colorless foam. (Ref. 0213)
HRMS Calcd 434.3032, Found 434.3039 (Ref. 0212)
1)Preparative TLC developed twice with AcOEt. 2)Preparative TLC developed twice with CH2Cl2-EtOH (10 : 1). (Ref. 0213)

Synthesis from dehydroepiandrostertone via the 5,7-diene by photochemical method. (Ref. 0212/0213)



69
(25R)-1a,25,26-trihydroxy-22-oxavitamin D3 / (25R)-1a,25,26-trihydroxy-22-oxacholecalciferol
(5Z,7E)-(1S,3R,25R)-22-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,25,26-tetrol
VVD0071
Sachiko Yamada
1a,25R,26-(OH)3-22-oxa-D3
C26H42O5 434.609 Download ChemDraw structure file
The antiproliferation activity towards HL-60 was 1/9 of 22-oxacalcitriol (OCT). The binding affinity for bovine thymus vitamin D receptor was 1/25 of OCT. (Ref. 0213)
[a]d-20 49.35 deg (c = 0.08 in EtOH) (Ref. 0212)
(EtOH) lmax (nm) 263, lmin (nm) 227 (Ref. 0212)
(neat) 3375, 2920, 2865, 1050 cm-1 (Ref. 0212)
1H-NMR (d, CDCl3) 0.53 (3H, s), 1.18 (3H, s), 1.20 (3H, d, J = 7.3 Hz), 3.25-3.57 (4H, m), 3.81-3.93 (1H, m), 4.23 (1H, br s), 4.43 (1H, br s), 4.42 (1H, br s), 4.99 (1H, s), 5.33 (1H, s), 6.02 (1H, d, J = 11.6 Hz), 6.37 (1H, d, J = 11.6 Hz) (Ref. 0212)
m/z 434 (M+), 85 (100%) (Ref. 0212)
Colorless foam. (Ref. 0213)
HRMS Calcd 434.3032, Found 434.3048 (Ref. 0212)
1)Preparative TLC developed twice with AcOEt-EtOH (25 : 1). 2)Preparative TLC developed with CH2Cl2-EtOH (20 : 3). (Ref. 0213)

Synthesis from dehydroepiandrostertone via the 5,7-diene by photochemical method. (Ref. 0212/0213)



70
(25S)-1a,25,26-trihydroxy-22-oxavitamin D3 / (25S)-1a,25,26-trihydroxy-22-oxacholecalciferol
(5Z,7E)-(1S,3R,25S)-22-oxa-9,10-seco-5,7,10(19)-cholestatriene-1,3,25,26-tetrol
VVD0072
Sachiko Yamada
1a,25S,26-(OH)3-22-oxa-D3
C26H42O5 434.609 Download ChemDraw structure file
The antiproliferation activity towards HL-60 was 1/7 of 22-oxacalcitriol (OCT). The binding affinity for bovine thymus vitamin D receptor was 1/30 of OCT. (Ref. 0213)
[a]d-20 65.85 deg (c = 0.09 in EtOH) (Ref. 0212)
(EtOH) lmax (nm) 264, lmin (nm) 227 (Ref. 0212)
(neat) 3385, 2920, 2865, 1050, 730 cm-1 (Ref. 0212)
1H-NMR (d, CDCl3) 0.54 (3H, s), 1.19 (3H, s), 1.19 (3H, d, J = 5.9 Hz), 3.21-3.34 (1H, m), 3.42 (2H, s), 3.44-3.61 (1H, m), 3.69-3.81 (1H, m), 4.22 (1H, br s), 4.43 (1H, br s), 5.00 (1H, s), 5.33 (1H, s), 6.02 (1H, d, J = 11.2 Hz), 6.37 (1H, d, J = 11.2 Hz) (Ref. 0212)
m/z 434 (M+), 85 (100%) (Ref. 0212)
Colorless foam. (Ref. 0213)
HRMS Calcd 434.3032, Found 434.3048 (Ref. 0212)
1)Preparative TLC developed twice with AcOEt-EtOH (25 : 1). 2)Preparative TLC developed with CH2Cl2-EtOH (20 : 3). (Ref. 0213)

Synthesis from dehydroepiandrostertone via the 5,7-diene by photochemical method. (Ref. 0212/0213)



71
25-azavitamin D3 / 25-azacholecalciferol
(5Z,7E)-(3S)-25-aza-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0073
Sachiko Yamada
25-aza-D3
C26H43NO 385.626 Download ChemDraw structure file

(EtOH) lmax (nm) 265 (Ref. 0360)
1H-NMR (d, CDCl3) 6.24 and 6.03 (2 H, AB, J = 11Hz, H-6 and -7), 5.05 (1 H, m, H-19), 4.82 (1 H, m, H-19), 3.95 (1 H, tt, J = 7.4 and 3.7 Hz, H-3), 2.31 (6 H, s, H-26 and 27), 0.93 (3 H, J = 6 Hz, H-21), 0.54 (3 H, s, H-18) (Ref. 0360)
m/z (rel. intensity) 385 (M+, 15), 370 (3), 352 (1), 84 (10), 71 (4), 58 (100) (Ref. 0360)



From C(22) tosyloxysteroid via reaction sith dimethyl acetamide as key step. (Ref. 0369)



72
1a,25-dihydroxy-23-azavitamin D3 / 1a,25-dihydroxy-23-azacholecalciferol
(5Z,7E)-(1S,3R)-23-aza-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0074
Sachiko Yamada
23-aza-1a,25-(OH)2D3
C26H43NO3 417.625 Download ChemDraw structure file
Differentiation inducing activity of HL-60 was shown in comparison with 1,25-(OH)2D3. (Ref. 0210)
(EtOH) lmax (nm) 263, lmin (nm) 227 (Ref. 0210)
1H-NMR (d, CDCl3) 0.57 (3H, s), 1.02 (3H, d, J = 6.2 Hz), 1.23 (6H, s), 2.51 (2H, s), 4.11-4.28 (1H, br),4.31-4.50 (1H, br), 4.99 (1H, s), 5.32 (1H, s), 6.01 (1H, d, J = 11.4 Hz), 6.37 (1H, d, J = 11.4 Hz) (Ref. 0210)
m/z 417 (M+), 43 (100%) (Ref. 0210)

Preparative TLC developed with CH2Cl2-EtOH (3 : 1). (Ref. 0210)

Synthesis from dehydroepiandrostertone via 5,7-diene compound by photochemical method. (Ref. 0210)



73
1a-hydroxy-24-(dimethylphosphoryl)-25,26,27-trinorvitamin D3 / 1a-hydroxy-24-(dimethylphosphoryl)-25,26,27-trinorcholecalciferol
(5Z,7E)-(1S,3R)-24-(dimethylphosphoryl)-9,10-seco-5,7,10(19)-cholatriene-1,3-diol
VVD0075
Sachiko Yamada
24-(dimethylphosphoryl)-1a-OH-25,26,27-trinor-D3
C26H43O3P 434.592 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Intestinal calcium absorption in chick, 0.3% ; Bone calcium mobilization in chick, 0.15% ; Competitive binding to the vitamin D receptor in chick intestine, 0.35% ; Inhibition of clonal growth of human leukemia cells (HL-60), ED50 was not reached. (Ref. 0238)
[a]D +33.1 deg (c = 0.95 in CH2Cl2) (Ref. 0283)
(EtOH) lmax (nm) (e) 265 (14700), 212 (12700) (Ref. 0283)
(Film) 3380, 2940, 2890, 1650, 1305, 1235, 1060 cm-1 (Ref. 0283)
1H-NMR (d, CD2Cl2, 500MHz) 6.34 (1H, d, J = 11.3 Hz), 6.02 (1H, d, J = 11.3 Hz), 5.29 (1H, m), 4.95 (1H, m), 4.36 (1H, dd, J = 4.3 and 7.9 Hz), 4.15 (1H, m), 2.83 (1H, m), 2.54 (1H, m), 2.26 (1H, dd, J = 6.5 and 13.3 Hz), 2.01-1.46 (16H, m), 1.42 (6H, d, J = 12.5 Hz), 1.36-1.16 (6H, m), 0.95 (3H, d, J = 6.5 Hz), 0.55 (3H, s) (Ref. 0283)
31P-NMR (d, CD2Cl2, 18.8MHz) 43.90 (Ref. 0283)




By Wittig-Horner coupling of upper half of the title compound with lower half phosphine oxide. (Ref. 0283)



74
24-(dimethoxyphosphoryl)-25,26,27-trinorvitamin D3 / 24-(dimethoxyphosphoryl)-25,26,27-trinorcholecalciferol
(5Z,7E)-(3S)-24-(dimethoxyphosphoryl)-9,10-seco-5,7,10(19)-cholatrien-3-ol
VVD0076
Sachiko Yamada
24-(dimethoxyphosphoryl)-25,26,27-trinor-D3
C26H43O4P 450.591 Download ChemDraw structure file

[a]D +27.0 deg (c = 0.73 in CH2Cl2) (Ref. 0283)
(EtOH) lmax (nm) (emax) 264 (14700) (Ref. 0283)
(Film) 3400, 2950, 2890, 1640, 1233, 1060, 1035 cm-1 (Ref. 0283)
1H-NMR (d, d6-acetone, 250MHz) 6.25 (1H, d, J = 11.2 Hz), 6.08 (1H, d, J = 11.2 Hz), 5.03 (1H, m), 4.75 (1H, m), 3.78 (1H, m), 3.64 (6H, d, J = 10.7 Hz), 2.91-1.04 (26H, m), 0.97 (3H, d, J = 6.0 Hz), 0.58 (3H, s) (Ref. 0283)
31P-NMR (d, d6-acetone, 18.8MHz) 35.56 (Ref. 0283)




By Wittig-Horner coupling of upper half of the title compound with lower half phosphine oxide. The upper half was prepared from CD-ring 24-iodide by reaction with trimethylphosphite. (Ref. 0283)



75
1a-hydroxy-24-(dimethoxyphosphoryl)-25,26,27-trinorvitamin D3 / 1a-hydroxy-24-(dimethoxyphosphoryl)-25,26,27-trinorcholecalciferol
(5Z,7E)-(1S,3R)-24-(dimethoxyphosphoryl)-9,10-seco-5,7,10(19)-cholatriene-1,3-diol
VVD0077
Sachiko Yamada
24-(dimethoxyphosphoryl)-1a-OH-25,26,27-trinor-D3
C26H43O5P 466.590 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Intestinal calcium absorption in chick, 0.2% ; Bone calcium mobilization in chick, 0.13% ; Competitive binding to the vitamin D receptor in chick intestine, 6.98% ; Inhibition of clonal growth of human leukemia cells (HL-60), ED50 was not reached. (Ref. 0238)
[a]D +38.3 deg (c = 0.98 in CH2Cl2) (Ref. 0283)
(EtOH) lmax (nm) (e) 264 (18100), 211 (17000) (Ref. 0283)
(Film) 3390, 2944, 2890, 1645, 1235, 1054, 1030 cm-1 (Ref. 0283)
1H-NMR (d, d6-acetone, 250MHz) 6.30 (1H, d, J = 11.1 Hz), 6.10 (1H, d, J = 11.1 Hz), 5.32 (1H, m), 4.87 (1H, m), 3.69 (6H, d, J = 10.7 Hz), 2.51 (1H, m), 2.29 (1H, m), 2.06-1.20 (22H, m), 0.97 (3H, d, J = 6.0 Hz), 0.92-0.90 (1H, m), 0.59 (3H, s) (Ref. 0283)
31P-NMR (d, d6-acetone, 18.8MHz) 35.69 (Ref. 0283)




By Wittig-Horner coupling of upper half of the title compound with lower half phosphine oxide. The upper half was prepared from CD-ring 24-iodide by reaction with trimethylphosphite. (Ref. 0283)



76
1a,25-dihydroxy-19-norvitamin D3 / 1a,25-dihydroxy-19-norcholecalciferol
(7E)-(1R,3R)-19-nor-9,10-seco-5,7-cholestadiene-1,3,25-triol
VVD0078
Sachiko Yamada
1a,25-(OH)2-19-nor-D3
C26H44O3 404.626 Download ChemDraw structure file
The affinity of the title compound for the intestinal vitamin D receptor and plasma vitamin D binding protein was 30% and 20% of that of 1,25-(OH)2D3, respectively. The in vitro effects on human promyeloid leukemia (HL-60 cell) differentiation and osteocalcin secretion by human osteosarcoma (MG-63) cells by the title compound were nearly identical to those of 1,25-(OH)2D3. The in vivo calcemic effects was less than 10% of that of 1,25-(OH)2D3. (Ref. 0222)









77
1,25-dihydroxy-2-nor-1,2-secovitamin D3 / 1,25-dihydroxy-2-nor-1,2-secocholecalciferol
(5Z,7E)-A-nor-(1,2)-(9,10)-diseco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0079
Sachiko Yamada
1,25-(OH)2-2-nor-1,3-seco-D3
C26H44O3 404.626 Download ChemDraw structure file






From 25,26-dehydro-8-enol triflate CD ring synthon and ring A precursor, 2-methyll-3-ethynyl-2,3-dehydro-d-butyrolactone. Coupling of the two precursors was followed by catalytic partial hydrogenation, oxymercuration-demercuration (25-hydroxy introduction), and DIBAL reduction afforded the title compound after spontaneous 1,7-hydrogen shift. (Ref. 0330)



78
26,26,26,27,27,27-hexadeuterio-1a-fluoro-25-hydroxy-16,17,23,23,24,24-hexadehydrovitamin D3 / 26,26,26,27,27,27-hexadeuterio-1a-fluoro-25-hydroxy-16,17,23,23,24,24-hexadehydrocholecalciferol
(5Z,7E)-(1S,3R)-26,26,26,27,27,27-hexadeuterio-1-fluoro-9,10-seco-5,7,10(19),16-cholestatetraen-23-yne-3,25-diol
VVD0080
Sachiko Yamada
1a-F-25-OH-16,17,23,23,24,24-hexadehydro-[26,26,26,27,27,27-2H]D3
C27H31D6FO2 418.532 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Intestinal calcium absorption in chick, 0.5% ; Bone calcium mobilization in chick, 0.2% ; Competitive binding to the vitamin D receptor in chick intetine, 5.3%, and HL-60 cells, 9.2% ; Inhibition of clonal growth of human leukemia cells (HL-60), 571%. (Ref. 0238)
Biological activity (% of 1,25-(OH)2D3 effect) : Intestinal calcium absorption in chick, 0.2% ; Bone calcium mobilization in chick, 0.02% ; Competitive binding to the vitamin D receptor in chick intetine, 26%, and in human leukemia (HL-60) cells, 55% ; Inhibition of clonal growth of HL-60 cells, 52% ; Differentiation of HL-60 cells, 103%. (Ref. 0239)









79
1a,26,26,26,27,27,27-heptafluoro-25-hydroxy-16,17,23,23,24,24-hexadehydrovitamin D3 / 1a,26,26,26,27,27,27-heptafluoro-25-hydroxy-16,17,23,23,24,24-hexadehydrocholecalciferol
(5Z,7E)-(1S,3R)-1,26,26,26,27,27,27-heptafluoro-9,10-seco-5,7,10(19),16-cholestatetraen-23-yne-3,25-diol
VVD0081
Sachiko Yamada
1a,26,26,26,27,27,27-F7-25-OH-16,17,23,23,24,24-hexadehydro-D3
C27H31F7O2 520.523 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Intestinal calcium absorption in chick, 0.5% ; Bone calcium mobilization in chick, 0.2% ; Competitive binding to the vitamin D receptor in chick intetine, 5.3%, and HL-60 cells, 9.2% ; Inhibition of clonal growth of human leukemia cells (HL-60), 571%. (Ref. 0238)









80
26,26,26,27,27,27-hexadeuterio-1a,25-dihydroxy-16,17,23,23,24,24-hexadehydrovitamin D3 / 26,26,26,27,27,27-hexadeuterio-1a,25-dihydroxy-16,17,23,23,24,24-hexadehydrocholecalciferol
(5Z,7E)-(1S,3R)-26,26,26,27,27,27-hexadeuterio-9,10-seco-5,7,10(19),16-cholestatetraen-23-yne-1,3,25-triol
VVD0082
Sachiko Yamada
[26,26,26,27,27,27-2H]-1a,25-(OH)2-16,17,23,23,24,24-hexadehydro-D3
C27H32D6O3 416.541 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Intestinal calcium absorption in chick, 0.4% ; Bone calcium mobilization in chick, 1.2% ; Competitive binding to the vitamin D receptor in chick intetine, 86%, and in human leukemia (HL-60) cells, 46% ; Inhibition of clonal growth of HL-60 cells, 233% ; Differentiation of HL-60 cells, 300%. (Ref. 0239)









81
26,26,26,27,27,27-hexafluoro-25-hydroxy-16,17,23,23,24,24-hexadehydrovitamin D3 / 26,26,26,27,27,27-hexafluoro-25-hydroxy-16,17,23,23,24,24-hexadehydrocholecalciferol
(5Z,7E)-(3S)-26,26,26,27,27,27-hexafluoro-9,10-seco-5,7,10(19),16-cholestatetraen-23-yne-3,25-diol
VVD0083
Sachiko Yamada
26,26,26,27,27,27-F6-25-OH-16,17,23,23,24,24-hexadehydro-D3
C27H32F6O2 502.532 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Intestinal calcium absorption in chick, 0.13 ; Bone calcium mobilization in chick, 2.0 ; Competitive binding to the vitamin D receptor in chick intetine, 0.58, and HL-60 cells, 2.03 ; Inhibition of clonal growth of human leukemia cells (HL-60), 72. (Ref. 0238)









82
26,26,26,27,27,27-hexafluoro-1a,25-dihydroxy-16,17,23,23,24,24-hexadehydrovitamin D3 / 26,26,26,27,27,27-hexafluoro-1a,25-dihydroxy-16,17,23,23,24,24-hexadehydrocholecalciferol
(5Z,7E)-(1S,3R)-26,26,26,27,27,27-hexafluoro-9,10-seco-5,7,10(19),16-cholestatetraen-23-yne-1,3,25-triol
VVD0084
Sachiko Yamada
26,26,26,27,27,27-F6-1a,25-(OH)2-16,17,23,23,24,24-hexadehydro-D3
C27H32F6O3 518.532 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Intestinal calcium absorption in chick, 6.7% ; Bone calcium mobilization in chick, 10.4% ; Competitive binding to the vitamin D receptor in chick intetine, 45%, and HL-60 cells, 31% ; Inhibition of clonal growth of human leukemia cells (HL-60), 8000%. (Ref. 0238)









83
26,26,26,27,27,27-hexafluoro-25-hydroxy-23,23,24,24-tetradehydrovitamin D3 / 26,26,26,27,27,27-hexafluoro-25-hydroxy-23,23,24,24-tetradehydrocholecalciferol
(5Z,7E)-(3S)-26,26,26,27,27,27-hexafluoro-9,10-seco-5,7,10(19)-cholestatrien-23-yne-1,25-diol
VVD0086
Sachiko Yamada
26,26,26,27,27,27-F6-25-OH-23,23,24,24-tetradehydro-D3
C27H34F6O2 504.548 Download ChemDraw structure file
(% of 1,25-(OH)2D3 effect) Affinity for chick intestinal receptor: 0.18%; Affinity for human vitamin D binding protein: 470%. (Ref. 0359)









84
26,26,26,27,27,27-hexafluoro-1a,25-dihydroxy-23,23,24,24-tetradehydrovitamin D3 / 26,26,26,27,27,27-hexafluoro-1a,25-dihydroxy-23,23,24,24-tetradehydrocholecalciferol
(5Z,7E)-(1S,3R)-26,26,26,27,27,27-hexafluoro-9,10-seco-5,7,10(19)-cholestatrien-23-yne-1,3,25-triol
VVD0087
Sachiko Yamada
26,26,26,27,27,27-F6-1a,25-(OH)2-23,23,24,24-tetradehydro-D3
C27H34F6O3 520.547 Download ChemDraw structure file
Cell differentiation: 10 times as active as 1,25-(OH)2D3 ; hypercalcemic activity: 2 times as active as 1,25-(OH)2D3. (Ref. 0356)









85
(22E)-26,26,26,27,27,27-hexadeuterio-1a,25-dihydroxy-22,23-didehydrovitamin D3 / (22E)-26,26,26,27,27,27-hexadeuterio-1a,25-dihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R)-26,26,26,27,27,27-hexadeuterio-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,25-triol
VVD0088
Sachiko Yamada
(22E)-1a,25-(OH)2-22,23-didehydro-[26,26,26,27,27,27-2H]D3
C27H36D6O3 420.573 Download ChemDraw structure file










86
24,24,26,26,26,27,27,27-octadeuterio-1a,25-dihydroxyvitamin D3 / 24,24,26,26,26,27,27,27-octadeuterio-1a,25-dihydroxycholecalciferol
(5Z,7E)-(1S,3R)-24,24,26,26,26,27,27,27-octadeuterio-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0089
Sachiko Yamada
1a,25-(OH)2-[24,24,26,26,26,27,27,27-2H]D3
C27H36D8O3 424.573 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Intestinal calcium absorption in rat, 106 ; Bone calcium mobilization in rat, 147 ; Competitive binding to rat intestinal vitamin D receptor, 100 ; Differentiation of human leukemia cells (HL-60), 100. (Ref. 0237)









87
(22E)-26,26,26,27,27,27-hexafluoro-25-hydroxy-22,23-didehydrovitamin D3 / (22E)-26,26,26,27,27,27-hexafluoro-25-hydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(3S)-26,26,26,27,27,27-hexafluoro-9,10-seco-5,7,10(19),22-cholestatetraene-3,25-diol
VVD0090
Sachiko Yamada
26,26,26,27,27,27-F6-25-OH-22,23-didehydro-D3
C27H36F6O2 506.564 Download ChemDraw structure file

(EtOH) lmax (nm) 264, lmin (nm) 228 (Ref. 0197)

m/z 506, 473, 271, 253, 136, 118 (Ref. 0197)



The provitamin D constructed from hexafluoro C(5) side chain sulfone and C(22)-steroid aldehyde was converted to the title vitamin D compound by photochemical method. (Ref. 0197)



88
(22E)-26,26,26,27,27,27-hexafluoro-1a,25-dihydroxy-22,23-didehydrovitamin D3 / (22E)-26,26,26,27,27,27-hexafluoro-1a,25-dihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R)-26,26,26,27,27,27-hexafluoro-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,25-triol
VVD0091
Sachiko Yamada
(22E)-26,26,26,27,27,27-F6-1a,25-(OH)2-22,23-didehydro-D3
C27H36F6O3 522.563 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Intestinal calcium absorption in rat, 221 ; Bone calcium mobilization in rat, 110 ; Competitive binding to rat intestinal vitamin D receptor, 62 ; Differentiation of human leukemia cells (HL-60), 3000. (Ref. 0237)









89
(23E)-26,26,26,27,27,27-hexafluoro-1a,25-dihydroxy-23,24-didehydrovitamin D3 / (23E)-26,26,26,27,27,27-hexafluoro-1a,25-dihydroxy-23,24-didehydrocholecalciferol
(5Z,7E,23E)-(1S,3R)-26,26,26,27,27,27-hexafluoro-9,10-seco-5,7,10(19),23-cholestatetraene-1,3,25-triol
VVD0092
Sachiko Yamada
(23E)-26,26,26,27,27,27-F6-1a,25-(OH)2-23,24-didehydro-D3
C27H36F6O3 522.563 Download ChemDraw structure file
Differentiation of HL-60 cells: 10 times more potent than 1,25-(OH)2D3.(Ref. 0356)









90
26,26,26,27,27,27-hexadeuterio-1a,25-dihydroxyvitamin D3 / 26,26,26,27,27,27-hexadeuterio-1a,25-dihydroxycholecalciferol
(5Z,7E)-(1S,3R)-26,26,26,27,27,27-hexadeuterio-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0093
Sachiko Yamada
1a,25-(OH)2-[26,26,26,27,27,27-2H]D3
C27H38D6O3 422.589 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Intestinal calcium absorption in rat, 92 ; Bone calcium mobilization in rat, 64 ; competitive binding to rat intestinal vitamin D receptor, 100 ; differentiation of human leukemia cells (HL-60), 100. (Ref. 0237)
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for rat intestinal receptor : 100 ; Calf intestinal receptor: 100; Intestinal calcium absorption, 92 ; Bone calcium mobilization, 64. (Ref. 0329)
1H-NMR (d, CD2Cl2) 6.33 and 5.98 (2H, AB pattern, d, J = 12.4 Hz, 6- and 7-H), 5.26 (1H, m, 19E-H), 4.93 (1H, br s, 19Z-H), 4.34 (1H, m, 1-H), 4.13 (1H, m, 3-H), 0.90 (3H, d, J = 6.2 Hz, 21C-CH3), 0.51 (3H, s, 18C-CH3) (Ref. 0195)
13C-NMR (d, CD2Cl2) 148.7 (C), 143.5 (C), 133.9 (C), 125.1 (CH), 117.6 (CH), 111.8 (C-19), 71.2 (CH), 70.8, 67.2 (CH), 57.1, 56.8, 46.3, 45.8, 44.8, 43.5, 40.9, 36.9, 36.5, 29.4, 28.0, 24.0, 22.6, 21.2, 19.0, 12.1 (Ref. 0195)




The upper half was synthesized from CD-ring 8,22-diol 22-tosylate via introduction of acetylene unit, reaction with acetone-d6, catalytic hydrogenation, and oxidation. Wittig-Horner coupling of the upper half synthon with ring A phosphine oxide afforded the title compound. (Ref. 0329)
From protected 1a-hydroxy-26,27-dinorvitamin D3 25-carboxylate via reaction with CD3MgI. (Ref. 0195)



91
1a-fluoro-25-hydroxy-16,17,23,23,24,24-hexadehydrovitamin D3 / 1a-fluoro-25-hydroxy-16,17,23,23,24,24-hexadehydrocholecalciferol
(5Z,7E)-(1S,3R)-1-fluoro-9,10-seco-5,7,10(19),16-cholestatetraen-23-yne-3,25-diol
VVD0094
Sachiko Yamada
1a-F-25-OH-16,17,23,23,24,24-hexadehydro-D3
C27H37FO2 412.580 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Intestinal calcium absorption in chick, 0.03 ; Bone calcium mobilization in chick, 0.08 ; Competitive binding to the vitamin D receptor in chick intetine, 24, and in human leukemia (HL-60) cells, 35 ; Inhibition of clonal growth of HL-60 cells, 61 ; Differentiation of HL-60 cells, 417. (Ref. 0239)









92
26,26,26,27,27,27-hexafluoro-1aa-hydroxyvitamin D3 / 26,26,26,27,27,27-hexafluoro-1aa-hydroxycholecalciferol
(5Z,7E)-(1S,3R)-26,26,26,27,27,27-hexafluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0095
Sachiko Yamada
26,26,26,27,27,27-F6-1a-OHD3
C27H38F6O2 508.580 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Binding affinity for chick intestinal and HL-60 cell receptor : both 1.4. Inhibition of proliferation and induction of differentiation of HL-60 cells : 100. (Ref. 0247)









93
26,26,26,27,27,27-hexafluoro-25-hydroxyvitamin D3 / 26,26,26,27,27,27-hexafluoro-25-hydroxycholecalciferol
(5Z,7E)-(3S)-26,26,26,27,27,27-hexafluoro-9,10-seco-5,7,10(19)-cholestatriene-3,25-diol
VVD0096
Sachiko Yamada
26,26,26,27,27,27-F6-25-OHD3
C27H38F6O2 508.580 Download ChemDraw structure file
The title compound was equipotent with 25-OHD3 in stimulating intestinal calcium transport, bone calcium mobilization, bone mineralization, epiphyseal plate calcification, and elevation of serum inorganic phosphorus. Bilateral nephrectomy eliminates the response of intestine and bone to this compound suggesting that this compound must be 1a-hydroxylated to be functional. (Ref. 0305)
(EtOH) lmax (nm) (emax) 264 (18000) lmin (nm) (emin) 227.5 (8600) (Ref. 0200)

m/z 508 (M+), 493, 490, 476, 271, 253, 136, 118 (Ref. 0200)



From 24-tosyloxy-5-cholene derivative via reaction of 24-sulfone with trifluoroacetone as key step. (Ref. 0200)



94
6,19-epidioxy-26,26,26,27,27,27-hexafluoro-25-hydroxy-6,19-dihydrovitamin D3 / 6,19-epidioxy-26,26,26,27,27,27-hexafluoro-25-hydroxy-6,19-dihydrocholecalciferol
(7E)-(3S)-6,19-epidioxy-26,26,26,27,27,27-hexafluoro-9,10-seco-5(10),7-cholestadiene-3,25-diol
VVD0097
Sachiko Yamada
6,19-epidioxy-26,26,26,27,27,27-F6-25-OH-6,19-dihydro-D3
C27H38F6O4 540.579 Download ChemDraw structure file
Binding affinity for the vitamin D receptor in HL-60 cells : 1/1500 as active as 1,25-(OH)2D3. Differentiation of HL-60 cells : 1/30 as active as 1,25-(OH)2D3. (Ref. 0339)

m/z 540 (M+), 522, 508, 504, 402, 384, 371, 330, 285 (Ref. 0339)



As a major product by the reaction of 26,26,26,27,27,27-hexafluoro-25-hydroxyvitamin D3 with singlet oxygen generated by dye-sensitized photochemical method. (Ref. 0339)



95
26,26,26,27,27,27-hexafluoro-1a,24-dihydroxyvitamin D3 / 26,26,26,27,27,27-hexafluoro-1a,24-dihydroxycholecalciferol
(5Z,7E)-(1S,3R)-26,26,26,27,27,27-hexafluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0098
Sachiko Yamada
26,26,26,27,27,27-F6-1a,24-(OH)2D3
C27H38F6O3 524.579 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Binding affinity for chick intestinal and HL-60 cell receptor : 66 and 100, respectively. Inhibition of proliferation and induction of differentiation of HL-60 cells : 1000. (Ref. 0247)









96
26,26,26,27,27,27-hexafluoro-1a,25-dihydroxyvitamin D3 / 26,26,26,27,27,27-hexafluoro-1a,25-dihydroxycholecalciferol
(5Z,7E)-(1S,3R)-26,26,26,27,27,27-hexafluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0099
Sachiko Yamada
26,26,26,27,27,27-F6-1a,25-(OH)2D3
C27H38F6O3 524.579 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Intestinal calcium absorption in rat, 229 ; Bone calcium mobilization in rat, 137 ; Competitive binding to rat intestinal vitamin D receptor, 82 ; Differentiation of human leukemia cells (HL-60), 2000. (Ref. 0237)
Biological activity (% of 1,25-(OH)2D3 effect) : Binding affinity for chick intestinal and HL-60 cell receptor : 33 and 100, respectively. Inhibition of proliferation and induction of differentiation of HL-60 cells : 1000. (Ref. 0247)
The activity to induce vitamin D 24-hyddroxylase in HL-60 cells : 4 times as potent as 1,25-(OH)2D3. (Ref. 0269)
lmax (nm) 264.5, lmin (nm) 228 (Ref. 0287)

m/z 524 (M+), 506, 488, 473, 462, 383, 287, 269, 251, 152, 134 (Ref. 0287)



From cholenic acid via reaction of 24-sulfone derivative with hexafluoroacetone as key step. (Ref. 0287)
Metabolism of 26,27-F6-1,25-(OH)2D3 in vitamin D-deficient rat was studied and 26,26,26,27,27,27-hexafluoro-1,23S,25-trihydroxyvitamin D3 was idenfified as major metabolite found in intestine (Ref. 0270)
In HL-60 cells pre-treated with 10-9 M 26,27-F6-1,25-(OH)2D3, 26,27-F6-1,25-(OH)2[1b-3H]D3 was mainly metabolized to 26,26,26,27,27,27-hexafluoro-1,23S,25-trihydroxyvitamin D3. (Ref. 0269)


97
(23S)-26,26,26,27,27,27-hexafluoro-1a,23,25-trihydroxyvitamin D3 / (23S)-26,26,26,27,27,27-hexafluoro-1a,23,25-trihydroxycholecalciferol
(5Z,7E)-(1S,3R,23S)-26,26,26,27,27,27-hexafluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,23,25-tetrol
VVD0100
Sachiko Yamada
26,26,26,27,27,27-F6-1a,23S,25-(OH)3D3
C27H38F6O4 540.579 Download ChemDraw structure file
Binding affinity for chick intestinal receptor: 2-3 times less active than 1,25-(OH)2 D3 ; Intestinal calcium transport: comparable to 1,25-(OH)2 D3.. (Ref. 0270)

TMS ether: spectrum (Ref. 0270)

HPLC: (Ref. 0270)


Major intestinal metabolite produced from 26,27-F6 -1,25-(OH)2 D3 . (Ref. 0270)


98
25-hydroxy-16,17,23,23,24,24-hexadehydrovitamin D3 / 25-hydroxy-16,17,23,23,24,24-hexadehydrocholecalciferol
(5Z,7E)-(3S)-9,10-seco-5,7,10(19),16-cholestatetraen-23-yne-3,25-diol
VVD0101
Sachiko Yamada
25-OH-16,17,23,23,24,24-hexadehydro-D3
C27H38O2 394.589 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Intestinal calcium absorption in rat, 72 ; Bone calcium mobilization in rat, 0 ; Competitive binding to rat intestinal vitamin D receptor, 0.07 ; Differentiation of human leukemia cells (HL-60), 1. (Ref. 0237)









99
(22E)-1a-hydroxy-24-oxo-26,27-cyclo-22,23-didehydrovitamin D3 / (22E)-1a-hydroxy-24-oxo-26,27-cyclo-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R)-1,3-dihydroxy-26,27-cyclo-9,10-seco-5,7,10(19),22-cholestatetraen-24-one
VVD0102
Sachiko Yamada
(22E)-1a-OH-24-oxo-22,23-didehydro-26,27-cyclo-D3
C27H38O3 410.589 Download ChemDraw structure file






From protected (5E)-1a-hydroxy-22-oxo-23,24,25,26,27-pentanorvitamin D3 via Wittig-Horner coupling with side chain fragment, followed by photochemical isomerization and deprotection. (Ref. 0289)
Isolated as a metabolite produced from 1a,24S-dihydroxy-26,27-cyclo-22,23-didehydrovitamin D3 (calcipotriol, MC903). (Ref. 0322)


100
24,25-epoxy-1a-hydroxy-22,22,23,23-tetradehydrovitamin D3 / 24,25-epoxy-1a-hydroxy-22,22,23,23-tetradehydrocholecalciferol
(5Z,7E)-(1S,3R)-24,25-epoxy-9,10-seco-5,7,10(19)-cholestatrien-22-yne-1,3-diol
VVD0103
Sachiko Yamada
24,25-epoxy-1a-OH-22,22,23,23-tetradehydro-D3 / 24,25-epoxy-1a-OH-22-yne-D3
C27H38O3 410.589 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for pig intestinal receptor and human vitamin D binding protein : 2 and 5 respectively. Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60), osteosarcoma (MG-63) and breast carcinoma (MCF-7) cells : 3, 100 and 20, respectively. Elevation of serum calcium, serum osteocalcin, bone calcium and duodenal calbindin in rachitic chicks : all <1. (Ref. 0240)





By epoxidation of the corresponding olefinic precursor which was constructed from Inhoffen-Lythgoe diol. (Ref. 0240)



101
25,26-epoxy-1a-hydroxy-23,23,24,24-tetradehydrovitamin D3 / 25,26-epoxy-1a-hydroxy-23,23,24,24-tetradehydrocholecalciferol
(5Z,7E)-(1S,3R)-25,26-epoxy-9,10-seco-5,7,10(19)-cholestatrien-23-yne-1,3-diol
VVD0104
Sachiko Yamada
25,26-epoxy-1a-OH-23,23,24,24-tetradehydro-D3 / 25,26-epoxy-1a-OH-23-yne-D3
C27H38O3 410.589 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for pig intestinal receptor and human vitamin D binding protein : 30 and 6 respectively. Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60), osteosarcoma (MG-63) and breast carcinoma (MCF-7) cells : 240, 150 and 127, respectively. Elevation of serum calcium, serum osteocalcin, bone calcium and duodenal calbindin in rachitic chicks : 1, 2, 0.4 and 2 ,respectively. (Ref. 0240)





By epoxidation of the corresponding olefinic precursor which was constructed from Inhoffen-Lythgoe diol. (Ref. 0240)



102
25,26-epoxy-1a-hydroxy-23,23,24,24-tetradehydro-20-epivitamin D3 / 25,26-epoxy-1a-hydroxy-23,23,24,24-tetradehydro-20-epicholecalciferol
(5Z,7E)-(1S,3R,20S)-25,26-epoxy-9,10-seco-5,7,10(19)-cholestatrien-23-yne-1,3-diol
VVD0105
Sachiko Yamada
25,26-epoxy-1a-OH-23,23,24,24-tetradehydro-20-epi-D3 / 25,26-epoxy-1a-OH-23-yne-20-epi-D3
C27H38O3 410.589 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for pig intestinal receptor and human vitamin D binding protein : 30 and 0, respectively. Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60), osteosarcoma (MG-63), and breast carcinoma (MCF-7) cells : 2000, 3000 and 4000, respectively. Elevation of serum calcium, serum osteocalcin, bone calcium, and duodenal calbindin in rachitic chicks : 3, 1, 1 and 1, respectively. (Ref. 0240)





By epoxidation of the corresponding olefinic precursor which was constructed from Inhoffen-Lythgoe diol. (Ref. 0240)



103
1a,25-dihydroxy-16,17,23,23,24,24-hexadehydrovitamin D3 / 1a,25-dihydroxy-16,17,23,23,24,24-hexadehydrocholecalciferol
(5Z,7E)-(1S,3R)-9,10-seco-5,7,10(19),16-cholestatetraen-23-yne-1,3,25-triol
VVD0106
Sachiko Yamada
1a,25-(OH)2-16,17,23,23,24,24-hexadehydro-D3
C27H38O3 410.589 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 10000 ; Intestinal calcium absorption in rat, 53 ; Bone calcium mobilization in rat, 0 ; Competitive binding to rat intestinal vitamin D receptor, 51; Differentiation of human leukemia cells (HL-60), 1000. (Ref. 0237)
Biological activity (% of 1,25-(OH)2D3 effect ) : Intestinal calcium absorption in chick, 3.3 ; Bone calcium mobilization in chick, 2 ; Competitive binding to the vitamin D receptor in chick intetine, 75, and HL-60 cells, 79. (Ref. 0238)
Survival of BALB/c mice received myeloid leukemic cells (WEHI 3BD+): Mice treated with the title compound (1.6 mg q.o.d.) had a significantly longer survival, with the last mouse dying of leukemia on day 50. (Ref. 0328)





By Wittig-horner coupling of upper CD-ring plus side chain part and the lower A-ring phophine oxide. The 16-ene CD-side chain part was synthesized from a 1-ethylideneperhydroindan derivative via ene reaction with 4-hydroxy-4-methylpentynal derivative as the key step. (Ref. 0358)



104
1a,25-dihydroxy[26,26,26,27,27,27-3H6]vitamin D3 / 1a,25-dihydroxy[26,26,26,27,27,27-3H6]cholecalciferol / [26,26,26,27,27,27-3H6]calcitriol
(5Z,7E)-(1S,3R)-[26,26,26,27,27,27-3H6]-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0107
Sachiko Yamada
1a,25-(OH)2-[26,26,26,27,27,27-3H6]D3 / [26,26,26,27,27,27-3H6]calcitriol
C27H38T6O3 428.589 Download ChemDraw structure file

lmax (95% EtOH) (nm) 262 (Ref. 0235)

m/z 428 (M+), 410 (M+-H2O, 9), 392 (M+-2H2O, 10), 287 (M+-side chain, 3), 285 (287-2H, 4), 269 (287-H2O, 5), 267 (285-H2O, 3), 152 (ring A plus carbons 6 and 7, 29), 134 (152-H2O, 100), 71 [(C3H3)2 C-OH]+, 100]; spectrum (Ref. 0235)

HPLC comparisons of 1a,25-(OH)2[26,27-3H]D3, prepared by chemical or enzymatic synthesis, to authentic unlabeled 1a,25-(OH)2D3. The UV peak of unlabeled 1a,25-(OH)2D3 was distinguishable from that of 1a,25-(OH)2[26,27-3H]D3.(Ref. 0235)

From 26,27-dinorvitamin D3 25-carboxylic acid via 1a-hydroxylation through 3,5-cyclovitamin D followed by treatment with [3H]methylmagnesium bromide [80 Ci/mmol) (Ref. 0235)



105
(22E)-(25R)-26,26,26-trideuterio-1a,25-dihydroxy-22,23-didehydrovitamin D3 / (22E)-(25R)-26,26,26-trideuterio-1a,25-dihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R,25R)-26,26,26-trideuterio-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,25-triol
VVD0108
Sachiko Yamada
(22E)-1a,25R-(OH)2-22,23-didehydro-[26,26,26-2H]D3
C27H39D3O3 417.597 Download ChemDraw structure file
Affinity for chick intestinal receptor: 133% of the effect of 1,25-(OH)2D3. (Ref. 0359)









106
(22E)-(25S)-26,26,26-trideuterio-1a,25-dihydroxy-22,23-didehydrovitamin D3 / (22E)-(25S)-26,26,26-trideuterio-1a,25-dihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R,25S)-26,26,26-trideuterio-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,25-triol
VVD0109
Sachiko Yamada
(22E)-1a,25S-(OH)2-22,23-didehydro-[26,26,26-2H]D3
C27H39D3O3 417.597 Download ChemDraw structure file
Affinity for chick intestinal receptor: 125% of the effect of 1,25-(OH)2D3. (Ref. 0359)









107
9,9,14,19,19-pentadeuterio-1a,25-dihydroxyvitamin D3 / 9,9,14,19,19-pentadeuterio-1a,25-dihydroxycholecalciferol
(5Z,7E)-(1S,3R)-9,9,14,19,19-pentadeuterio-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0110
Sachiko Yamada
1a,25-(OH)2-[9,9,14,19,19-2H]D3
C27H39D5O3 421.597 Download ChemDraw structure file
The activities of the title compound in binding to the chick and pig intestinal nuclear 1,25-(OH)2D3 receptors, in inducing differentiation of HL-60 cell, and inhibiting proliferation and inducing the production of osteocalcin in MG-63 cells were approximately same as those of 1,25-(OH)2D3. (Ref. 0226)





Convergent synthesis by combining upper-half fragment (9,14-dideuterio-25-hydroxy-des-AB-cholest-8-en-8-yl triflate) with lower-half fragment (silyl protected 19,19,19-trideuterio-1-ethynyl-2-methyl-1-cyclohexen-3S,5R-diol). The lower-half was synthesized starting from (S)-(+)-carvone and the upper half from Inhoffen-Lythgoe diol obtained by ozonolysis of vitamin D2. (Ref. 0231)



108
9,14,19,19,19-pentadeuterio-1a,25-dihydroxyprevitamin D3 / 9,14,19,19,19-pentadeuterio-1a,25-dihydroxyprecholecalciferol
(6Z)-(1S,3R)-9,14,19,19,19-pentadeuterio-9,10-seco-5(10),6,8-cholestatriene-1,3,25-triol
VVD0111
Sachiko Yamada
1a,25-(OH)2-pre-[9,14,19,19,19-2H]D3
C27H39D5O3 421.597 Download ChemDraw structure file
The title compound was as active as 1,25-(OH)2D3 in two nongenomic systems, transcaltachia as measured in the perfused chick kidney intestine and 45Ca2+ uptake through voltage-gated Ca2+ channels in ROS 17/2.8 cells. This compound was significantly less active both in binding in vitro to the plasma vitamin D-binding protein (7%) and to the chick (10%) and pig (4%) intestinal nuclear 1,25-(OH)2D3 receptors generating genomic biological responses in vivo (induction of plasma levels of osteocalcin, <5%) or in culture cells (inhibition of HL-60 cell differentiation, <5% ; inhibition of MG-63 proliferation, <2% ; and induction of osteocalcin, <2%). (Ref. 0226)





Convergent synthesis by combining upper-half synthon (9,14-dideuterio-25-hydroxy-des-AB-cholest-8-en-8-yl triflate) with lower-half synthon (silyl protected 19,19,19-trideuterio-1-ethynyl-2-methyl-1-cyclohexen-3S,5R-diol). The lower-half was synthesized starting from (S)-(+)-carvone and the upper half synthon from Inhoffen-Lythgoe diol obtained by ozonolysis of vitamin D2. (Ref. 0231)



109
(22E)-(25R)-26,26,26-trifluoro-1a,25-dihydroxy-22,23-didehydrovitamin D3 / (22E)-(25R)-26,26,26-trifluoro-1a,25-dihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R,25R)-26,26,26-trifluoro-9,10-seco-5,7,10(19),22-cholestatetraene-1,25-diol
VVD0112
Sachiko Yamada
(22E)-26,26,26-F3-1a,25R-(OH)2-22,23-didehydro-D3
C27H39F3O3 468.592 Download ChemDraw structure file
(% of 1,25-(OH)2D3 effect) Affinity for chick intestinal receptor: 57% (Ref. 0359); Induction of differentiation of HL-60 cells: 300% (Ref. 0356)









110
(22E)-(25S)-26,26,26-trifluoro-1a,25-dihydroxy-22,23-didehydrovitamin D3 / (22E)-(25S)-26,26,26-trifluoro-1a,25-dihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R,25S)-26,26,26-trifluoro-9,10-seco-5,7,10(19),22-cholestatetraene-1,25-diol
VVD0113
Sachiko Yamada
(22E)-26,26,26-F3-1a,25S-(OH)2-22,23-didehydro-D3
C27H39F3O3 468.592 Download ChemDraw structure file
(% of 1,25-(OH)2D3 effect) Affinity for chick intestinal receptor: 40% (Ref. 0359); Induction of differentiation of HL-60 cells: 4000% (Ref. 0356)









111
calicoferol A
(22E)-(8S)-3-hydroxy-9,10-seco-1,3,5(10),22-cholestatetraen-9-one
VVD0114
Sachiko Yamada
calicoferol A
C27H40O2 396.605 Download ChemDraw structure file
Toxic against brine shrimp larvae. (Ref. 0317)




Isolated from a gorgonian of the genus Calicogorgia. (Ref. 0318)




112
25-hydroxy-16,17,23,24-tetradehydrovitamin D3 / 25-hydroxy-16,17,23,24-tetradehydrocholecalciferol
(5Z,7E,23E)-(3S)-9,10-seco-5,7,10(19),16,23-cholestapentaene-3,25-diol
VVD0115
Sachiko Yamada
25-OH-16,17,23,24-tetradehydro-D3
C27H40O2 396.605 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Competitive binding to rat intestinal vitamin D receptor, 0.12 ; Differentiation of human leukemia cells (HL-60), 0.5. (Ref. 0237)









113
(23Z)-25-hydroxy-16,17,23,24-tetradehydrovitamin D3 / (23Z)-25-hydroxy-16,17,23,24-tetradehydrocholecalciferol
(5Z,7E,23Z)-(3S)-9,10-seco-5,7,10(19),16,23-cholestapentaene-3,25-diol
VVD0116
Sachiko Yamada
(23Z)-25-OH-16,17,23,24-tetradehydro-D3
C27H40O2 396.605 Download ChemDraw structure file
Affinity for rat intestinal receptor: 0.8%. (Ref. 0358)





From CD-ring plus side chain fragment and A-ring phosphine oxide by Wittig-Horner coupling. (Ref. 0358)



114
25-hydroxy-23,23,24,24-tetradehydrovitamin D3 / 25-hydroxy-23,23,24,24-tetradehydrocholecalciferol
(5Z,7E)-(3S)-9,10-seco-5,7,10(19)-cholestatrien-23-yne-3,25-diol
VVD0117
Sachiko Yamada
25-OH-23,23,24,24-tetradehydro-D3
C27H40O2 396.605 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Intestinal calcium absorption in rat, 71 ; Bone calcium mobilization in rat, 0 ; Competitive binding to rat intestinal vitamin D receptor, 0.06 ; Differentiation of human leukemia cells (HL-60), 1. (Ref. 0237)









115
1a-hydroxy-24-oxo-26,27-cyclovitamin D3 / 1a-hydroxy-24-oxo-26,27-cyclocholecalciferol
(5Z,7E)-(1S,3R)-1,3-dihydroxy-26,27-cyclo-9,10-seco-5,7,10(19)-cholestatrien-24-one
VVD0118
Sachiko Yamada
1a-OH-24-oxo-26,27-cyclo-D3
C27H40O3 412.605 Download ChemDraw structure file
(% of 1,25-(OH)2 D3effect) Affinity for calf thymus receptor: 0.5%; Transcriptional activity: 12.5%. (Ref. 0322)



HPLC chart. (Ref. 0322)


Produced as a metabolite of 1a,24S-dihydroxy-26,27-cyclo-22,23-didehydrovitamin D3 (Calcipotriol, VVD0121) and further metabolized to 23-hydroxylated compound. (Ref. 0322)


116
(22E)-25-hydroxy-24-oxo-22,23-didehydrovitamin D3 / (22E)-25-hydroxy-24-oxo-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(3S)-3,25-dihydroxy-9,10-seco-5,7,10(19),22-cholestatetraen-24-one
VVD0119
Sachiko Yamada
(22E)-25-OH-24-oxo-22,23-didehydro-D3
C27H40O3 412.605 Download ChemDraw structure file

(EtOH) lmax (nm) 265, lmin (nm) 228 (Ref. 0193)

high resoultion MS: m/z 412.2989 (Ref. 0193)



From Ergosterol via side chain introduction to 5,7-diene protected C(22)-aldehyde. (Ref. 0193)



117
(22E)-(24R)-1a,24-dihydroxy-26,27-cyclo-22,23-didehydrovitamin D3 / (22E)-(24R)-1a,24-dihydroxy-26,27-cyclo-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R,24R)-26,27-cyclo-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,24-triol
VVD0120
Sachiko Yamada
(22E)-1a,24R-(OH)2-26,27-cyclo-22,23-didehydro-D3
C27H40O3 412.605 Download ChemDraw structure file

Et2O-hexane :143-145 degC (Ref. 0289)
lmax (nm) (emax) 264 (17000) (Ref. 0289)
1H-NMR (d, CDCl3) 0.15-0.65 (4H, m), 0.56 (3H, s), 0.75-1.10 (1H, m), 1.05 (3H, d, J = 7.0 Hz), 3.47 (1H, m), 4.2 (1H, m), 4.4 (1H, m), 4.99 (1H, m), 5.31 (1H, m), 5.50 (2H, m), 5.99 and 6.36 (each 1H, d, J = 11.0 Hz) (Ref. 0289)
m/z 412 (M+, 5), 394 (8), 379 (1), 376 (5), 287 (5), 285 (6), 283 (7), 269 (10), 267 (5), 265 (4), 251 (10), 152 (27), 134 (100) (Ref. 0289)



From protected (5E)-1a-hydroxy-22-oxo-23,24,25,26,27-pentanorvitamin D3 via Wittig-Horner coupling with side chain fragment, reduction, separation of 24-epimers, photochemical isomerization and deprotection. (Ref. 0289)



118
(22E)-(24S)-1a,24-dihydroxy-26,27-cyclo-22,23-didehydrovitamin D3 / (22E)-(24S)-1a,24-dihydroxy-26,27-cyclo-22,23-didehydrocholecalciferol / Calcipotriol
(5Z,7E,22E)-(1S,3R,24S)-26,27-cyclo-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,24-triol
VVD0121
Sachiko Yamada
(22E)-1a,24S-(OH)2-26,27-cyclo-22,23-didehydro-D3
C27H40O3 412.605 Download ChemDraw structure file
Activity relative to 1,25-(OH)2D3 (defined 100%) : Affinity for the receptor in U937 cells (human histiocytic lymphoma cell line) : 200 ; Antiproliferative effects on U937 cells : 200 ; Induction of differentiation of U937 cells : 100 ; Calciuric effect: <0.5. (Ref. 0309)
This compound named calcipotriol (Leo laboratory code MC903) is the first active vitamin D analog to receive governmental approval to be used as an anti-proliferative agent in the treatment of psoriasis. (Ref. 0327)
(Methyl formate) 166-158 degC (Ref. 0289)
lmax (nm) (e) 264 (17200) (Ref. 0289)
1H-NMR (d, CDCl3) 0.15-0.65 (4H, m), 0.56 (3H, s), 0.75-1.10 (1H, m), 1.05 (3H, d, J = 7.0 Hz), 3.45 (1H, m), 4.2 (1H, m), 4.4 (1H, m), 4.99 (1H, m), 5.31 (1H, m), 5.47 (2H, m), 5.99 (1H, d, J = 11.0 Hz), 6.36 (1H, d, J = 11.0 Hz) (Ref. 0289)
m/z 412 (M+, 6), 394 (8), 379 (2), 376 (5), 287 (5), 285 (7), 283 (8), 269 (11), 267 (6), 265 (4), 251 (12), 152 (26), 134 (100) (Ref. 0289)



From protected (5E)-1a-hydroxy-22-oxo-23,24,25,26,27-pentanorvitamin D3 via Wittig-Horner coupling with side chain fragment, reduction, separation of 24-epimers, photochemical isomerization and deprotection. (Ref. 0289)
The in vitro metabolism of the title compound (calcipotriol) was studied in two keratinocyte cell models. Calcipotriol was initially converted into the 24-ketone and its 22,23-dihydro-derivative. Further metabolites such as two 23-epimeric 23-hydroxylated 22,23-dihydro-24-oxo-derivatives, two 23,24-dihydroxy-derivatives and side chain-cleavage products, tetranor-1,23-(OH)2D3 and calcitroic acid. (Ref. 0322)


119
(22E)-(24R)-1a,24-dihydroxy-26,27-cyclo-22,23-didehydro-20-epivitamin D3 / (22E)-(24R)-1a,24-dihydroxy-26,27-cyclo-22,23-didehydro-20-epicholecalciferol
(5Z,7E,22E)-(1S,3R,20S,24R)-26,27-cyclo-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,24-triol
VVD0122
Sachiko Yamada
(22E)-1a,24R-(OH)2-20-epi-22,23-didehydro-26,27-cyclo-D3 / (22E)-1a,24R-(OH)2-20-epi-22-ene-26,27-cyclo-D3
C27H40O3 412.605 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of U 937 cells, 130% ; Induction of differentiation of U 937 cells, 100% ; Calciuric effects on normal rats, <1%. (Ref. 0284)





From protected (5E)-22-oxo-23,24,25,26,27-pentanorvitamin D3 via side chain introduction by Wittig-Horner reaction followed by reduction, dye-sensitized photoisomerization and deprotection. (Ref. 0284)



120
(22E)-(24S)-1a,24-dihydroxy-26,27-cyclo-22,23-didehydro-20-epivitamin D3 / (22E)-(24S)-1a,24-dihydroxy-26,27-cyclo-22,23-didehydro-20-epicholecalciferol
(5Z,7E,22E)-(1S,3R,20S,24S)-26,27-cyclo-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,24-triol
VVD0123
Sachiko Yamada
(22E)-1a,24S-(OH)2-20-epi-22,23-didehydro-26,27-cyclo-D3 / (22E)-1a,24S-(OH)2-20-epi-22-ene-26,27-cyclo-D3
C27H40O3 412.605 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of U 937 cells, 60% ; Induction of differentiation of U 937 cells, 10% ; Calciuric effects on normal rats, <1%. (Ref. 0284)





From protected (5E)-22-oxo-23,24,25,26,27-pentanorvitamin D3 via side chain introduction by Wittig-Horner reaction followed by reduction, dye-sensitized photoisomerization and deprotection. (Ref. 0284)



121
(23E)-1a,25-dihydroxy-16,17,23,24-tetradehydrovitamin D3 / (23E)-1a,25-dihydroxy-16,17,23,24-tetradehydrocholecalciferol
(5Z,7E,23E)-(1S,3R)-9,10-seco-5,7,10(19),16,23-cholestapentaene-1,3,25-triol
VVD0124
Sachiko Yamada
1a,25-(OH)2-16,17,23,24-tetradehydro-D3
C27H40O3 412.605 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Competitive binding to rat intestinal vitamin D receptor, 80 ; Differentiation of human leukemia cells (HL-60), 300. (Ref. 0237)









122
(23Z)-1a,25-dihydroxy-16,17,23,24-tetradehydrovitamin D3 / (23Z)-1a,25-dihydroxy-16,17,23,24-tetradehydrocholecalciferol
(5Z,7E,23Z)-(1S,3R)-9,10-seco-5,7,10(19),16,23-cholestapentaene-1,3,25-triol
VVD0125
Sachiko Yamada
(23Z)-1a,25-(OH)2-16,17,23,24-tetradehydro-D3 / (23Z)-1a,25-(OH)2-16,23-diene-D3
C27H40O3 412.605 Download ChemDraw structure file
(% of 1,25-(OH)2D3 effect) Affinity for rat intestinal receptor: 145%; Affinity for human vitmin D binding protein: 17%; HL-60 cell differentiation: 100. (Ref. 0359)









123
(22R)-1a,25-dihydroxy-22,23,23,24-tetradehydrovitamin D3 / (22R)-1a,25-dihydroxy-22,23,23,24-tetradehydrocholecalciferol
(5Z,7E)-(1S,3R,22R)-9,10-seco-5,7,10(19),22,23-cholestapentaene-1,3,25-triol
VVD0126
Sachiko Yamada
(22R)-1a,25-(OH)2-22,23,23,24-tetradehydro-D3
C27H40O3 412.605 Download ChemDraw structure file
(% of 1,25-(OH)2D3 effect) Affinity for chick intestinal receptor: 52%; Affinity for human vitmin D binding protein: 48%. (Ref. 0359)









124
(22S)-1a,25-dihydroxy-22,23,23,24-tetradehydrovitamin D3 / (22S)-1a,25-dihydroxy-22,23,23,24-tetradehydrocholecalciferol
(5Z,7E)-(1S,3R,22S)-9,10-seco-5,7,10(19),22,23-cholestapentaene-1,3,25-triol
VVD0127
Sachiko Yamada
(22S)-1a,25-(OH)2-22,23,23,24-tetradehydro-D3
C27H40O3 412.605 Download ChemDraw structure file
(% of 1,25-(OH)2D3 effect) Affinity for chick intestinal receptor: 21%; Affinity for human vitmin D binding protein: 25%. (Ref. 0359)









125
1a,25-dihydroxy-23,23,24,24-tetradehydrovitamin D3 / 1a,25-dihydroxy-23,23,24,24-tetradehydrocholecalciferol
(5Z,7E)-(1S,3R)-9,10-seco-5,7,10(19)-cholestatrien-23-yne-1,3,25-triol
VVD0128
Sachiko Yamada
1a,25-(OH)2-23,23,24,24-tetradehydro-D3
C27H40O3 412.605 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Intestinal calcium absorption in rat, 95 ; Bone calcium mobilization in rat, 15 ; Competitive binding to rat intestinal vitamin D receptor, 39 ; Differentiation of human leukemia cells (HL-60), 300. (Ref. 0237)









126
(22E,24E)-1a,26a-dihydroxy-22,23,24,25-tetradehydro-26a-homo-27-norvitamin D3 / (22E,24E)-1a,26a-dihydroxy-22,23,24,25-tetradehydro-26a-homo-27-norcholecalciferol
(5Z,7E,22E,24E)-(1S,3R)-26a-homo-27-nor-9,10-seco-5,7,10(19),22,24-cholestapentaene-1,3,26a-triol
VVD0129
Sachiko Yamada
(22E,24E)-1a,26a-(OH)2-22,23,24,25-tetradehydro-26a-homo-27-nor-D3
C27H40O3 412.605 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of U937 cells, 300% ; Induction of differentiation of U 937 cells, 200% ; Calciuric activity, 1%. (Ref. 0288)





From protected (5E)-1a-hydroxy-22-oxo-23,24,25,26,27-pentanorvitamin D3 via side chain introduction by Wittig reaction, reduction, photoisomerization and deprotection. (Ref. 0288)



127
(23R,25R)-25-hydroxyvitamin D3 26,23-lactone / (23R,25R)-25-hydroxycholecalciferol 26,23-lactone
(5Z,7E)-(3S,23R,25R)-3,25-dihydroxy-9,10-seco-5,7,10(19)-cholestatrieno-26,23-lactone
VVD0130
Sachiko Yamada
25R-OHD3 26,23R-lactone
C27H40O4 428.604 Download ChemDraw structure file

lmax (nm) 265 (Ref. 0117)
1H-NMR (d, CDCl3, 400MHz) 6.23, 6.02 (2H, AB q, J = 10 Hz, 6-, 7-H), 5.04, 4.81 (2H, m, 19-H), 4.77 (1H, m, 23-H), 3.96 (1H, m, 3a-H), 1.52 (3H, s, 27-H), 1.02 (3H, d, J = 6 Hz, 21-H), 0.57 (3H, s, 18-H) (Ref. 0117)
m/z 428 (M+, 98), 413 (M+-Me, 6), 411 (6), 410 (M+-H2O, 22), 395 (M+-H2O-Me, 100), 369 (28), 253 (54) (Ref. 0117)



Synthesis from C(22) steroid aldehyde via iodolactonization of 22-ene-26-carboxylic acid as a key step. (Ref. 0117/0122)
Stereoselective synthesis of 23-epimers of 25R-OHD3 26,23-lactones from C(22)-steroid aldehyde and chiral side chain synthon prepared from (R)-citramalic acid. (Ref. 0113)



128
(23S,25R)-25-hydroxyvitamin D3 26,23-lactone / (23S,25R)-25-hydroxycholecalciferol 26,23-lactone
(5Z,7E)-(3S,23S,25R)-3,25-dihydroxy-9,10-seco-5,7,10(19)-cholestatrieno-26,23-lactone
VVD0131
Sachiko Yamada
25R-OHD3 26,23S-lactone
C27H40O4 428.604 Download ChemDraw structure file
Dose-response of 25-OHD3-26,23-lactone on intestinal calcium transport and bone calcium mobilization in vitamin D-deficient rats on a low calcium diet.: Table (Ref. 0112)
Effect of prior dosing of 25-OHD3-26,23-lactone on intestinal calcium transport and bone calcium mobilizing activity of 1,25-(OH)2D3 in vitamin D-deficient rats.: Table (Ref. 0112)
Ability of 25-OHD3 and 25-OHD3-26,23 lactone stereoisomers to competitively inhibit binding of 25-OH[3H]D3 to the 4.2s rat plasma vitamin D binding protein and competitively inhibit 1,25-(OH)2[3H]D3 binding to the 3.7s 1,25-(OH)2D3 cytosol receptor: Table (Ref. 0119)
lmax (nm) 264, lmin (nm) 229 (Ref. 0111)
lmax(nm) 265, lmin (nm) 228 (Ref. 0115)
(CCl4) 1784 cm-1 (Ref. 0115)
1H-NMR (d, CDCl3) spectrum (Ref. 0111)
1H-NMR (d, CDCl3) 6.28 (1H, d, J = 11.8 Hz, C-6), 6.03 (1H, d, J = 10.7 Hz, C-7), 5.05 (1H, m, C-19E), 4.82 (1H, m, C-19Z), 4.44 (1H, m, C-23), 3.96 (1H, m, C-3), 1.49 (3H, s, C-27), 1.03 (3H, d, J = 5.2 Hz, C-21), 0.56 (3H, s, C-18) (Ref. 0115)
1H-NMR (d, CDCl3, 400 MHz) 6.22, 6.03 (2H), 5.05 (1H), 4.82 (1H), 4.43 (1H), 3.95 (1H), 1.51 (3H), 1.03 (3H), 0.56 (3H) (Ref. 0117)
m/z 428 (27.6, M+), 410 (4.1, M+-H2O), 395 (12.0, M+-H2O-CH3), 271 (4.5, M+-side chain), 253 (9.3, M+-side chain-H2O), 136 (100, A ring+C6+C7+ : A ring fragment+) 118 (94, A ring fragment+-H2O) spectrum (Ref. 0111)
m/z 428.2919 (calcd, 428.2926) (26%, M+), 410 (2%, M+-H2O), 395 (9%, M+-H2O-CH3). 271 (1%, M+-side chain), 253 (8%, M+-side chain-H2O), 136 [100%, (A ring+C6+C7)+], 118 [83%, (A ring+C6+C7)+-H2O] (Ref. 0115)
m/z 428 (97, M+), 413 (10), 411 (9), 410 (25), 395 (100), 369 (28), 253 (22) (Ref. 0117)
CD : four isomers (23S,25S) [q]230 = 3.04 times 103, (23R,25R) [q]230 = 4.95 times 104, (23S,25R) [q]225 = -8.08 times 102, (23R,25S) [q]225 = -3.7 times 103.; spectra (Ref. 0114)
HPLC : (Ref. 0114)
Isolation and Identification from blood plasma of Chickens given either maintenance leueles or large doses of vitamin D3. (Ref. 0111)
Isolation and identification from vitamin D supplemented rat kidney homogenates incubated with 24,25-(OH)2D3. (Ref. 0118)
Stereoselective synthesis starting with C(22)-steroid aldehyde and chiral C(5)-side chain synthon (Ref. 0113/0123) and determination of the stereochemistry at C(23) and C(25) of natural metabolite.(Ref. 0113)
Synthesis of four diastereomers at C(23) and C(25) of 25-OHD3 26,23-lactone from C(22) steroid and the determination of the stereochemistry of the natural product. (Ref. 0114)
Synthesis of four diastereomers at C(23) and C(25) of 25-OHD3 26,23-lactone from 3b-acetoxy-24-nor-5,7-choladien-23-carboxylic acid ester. (Ref. 0115)
Synthesis of four diastereomers at C(23) and C(25) of 25-OHD3 26,23-lactone from C(22) steroid aldehyde via vinylation and orthoester claisen rearrangement as a key step. The stereochemistries at C(23) and C(25) were determined by X-ray analysis. (Ref. 0116/0117)
All four possible stereoisomers of 25-OHD3 26,23-lactone were synthesized from norcholadienoic acid. (Ref. 0121)
The role of kidney in the production of 25-OHD3 26,23-lactone and 1,25-(OH)2D3 26,23-lactone was demonstrated. (Ref. 0120)


129
(23R,25S)-25-hydroxyvitamin D3 26,23-lactone / (23R,25S)-25-hydroxycholecalciferol 26,23-lactone
(5Z,7E)-(3S,23R,25S)-3,25-dihydroxy-9,10-seco-5,7,10(19)-cholestatrieno-26,23-lactone
VVD0132
Sachiko Yamada
25S-OHD3 26,23R-lactone
C27H40O4 428.604 Download ChemDraw structure file

lmax (nm) 265 (Ref. 0117/0123)
(CHCl3) 1772 cm-1 (Ref. 0123)
1H-NMR (d, CDCl3, 400MHz) 6.22, 6.03 (2H, AB q, J = 10 Hz, 6-, 7-H), 5.04, 4.80 (2H, m, 19-H), 4.45 (1H, m, 23-H), 3.94 (1H, m, 3a-H), 1.51 (3H, s, 27-H), 1.01 (3H, d, J = 6 Hz, 21-H), 0.56 (3H, s, 18-H). (Ref. 0117)
1H-NMR (d, CDCl3) 0.57 (3H, s, 18-H), 1.01 (3H, d, J = 6 Hz, 21-H), 1.50 (3H, s, 27-H), 3.97 (1H, m, 3a-H), 4.45 (1H, m, 23-H), 4.83 (1 H, br s, H-19), 5.06 (1 H, br s, H-19), 6.13 (2 H, ABq, J = 11 Hz, H-6 and 7). (Ref. 0123)
m/z 428 (M+, 98), 413 (M+-Me, 7), 411 (6), 410 (M+-H2O, 21), 395 (M+-H2O-Me, 100), 369 (34), 253 (54) (Ref. 0117)
m/z 428 (M+), 410, 395, 369, 136, 118. (Ref. 0123)



Stereoselective synthesis of 25S-OHD3 26,23-lactone from C(22)-steroid aldehyde and chiral side chain synthon prepared from (S)-citramalic acid. (Ref. 0123)
Synthesis from C(22) steroid aldehyde via iodolactonization of 22-ene-26-carboxylic acid as a key step. (Ref. 0117)



130
(23S,25S)-25-hydroxyvitamin D3 26,23-lactone / (23S,25S)-25-hydroxycholecalciferol 26,23-lactone
(5Z,7E)-(3S,23S,25S)-3,25-dihydroxy-9,10-seco-5,7,10(19)-cholestatrieno-26,23-lactone
VVD0133
Sachiko Yamada
25S-OHD3 26,23S-lactone
C27H40O4 428.604 Download ChemDraw structure file

lmax (nm) 265 (Ref. 0117)
1H-NMR (d, CDCl3, 400MHz) 6.22, 6.02 (2H, AB q, J = 10 Hz, 6-, 7-H), 5.04, 4.80 (2H, m, 19-H), 4.72 (1H, m, 23-H), 3.95 (1H, m, 3a-H), 1.52 (3H, s, 27-H), 1.03 (3H, d, J = 6 Hz, 21-H), 0.57 (3H, s, 18-H) (Ref. 0117)
m/z 428 (M+, 100), 413 (M+-Me, 8), 411 (7), 395 (M+-H2O-Me, 71), 369 (15), 253 (10) (Ref. 0117)



Synthesis from C(22) steroid aldehyde via iodolactonization of 22-ene-26-carboxylic acid as a key step. (Ref. 0117)



131
(22E)-(24R,25R)-25,26-epoxy-1a,24-dihydroxy-22,23-didehydrovitamin D3 / (22E)-(24R,25R)-25,26-epoxy-1a,24-dihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R,24R,25R)-25,26-epoxy-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,24-triol
VVD0134
Sachiko Yamada
(22E)-25R,26-epoxy-1a,24R-(OH)2-22,23-didehydro-D3 / (22E)-25R,26-epoxy-1a,24R-(OH)2-22-ene-D3
C27H40O4 428.604 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for pig intestinal receptor and human vitamin D binding protein : 8 and 2 respectively. Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60), osteosarcoma (MG-63) and breast carcinoma (MCF-7) cells : 30, 140 and 22, respectively. Elevation of serum calcium, serum osteocalcin, bone calcium and duodenal calbindin in rachitic chicks : 1, 3, 2 and 1, respectively. (Ref. 0240)





By Sharpless kinetic epoxidation of the corresponding olefinic precursor. (Ref. 0243)



132
(22E)-(24S,25S)-25,26-epoxy-1a,24-dihydroxy-22,23-didehydrovitamin D3 / (22E)-(24S,25S)-25,26-epoxy-1a,24-dihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R,24S,25S)-25,26-epoxy-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,24-triol
VVD0135
Sachiko Yamada
(22E)-25S,26-epoxy-1a,24S-(OH)2-22,23-didehydro-D3 / (22E)-25S,26-epoxy-1a,24S-(OH)2-22-ene-D3
C27H40O4 428.604 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for pig intestinal receptor and human vitamin D binding protein : 8 and 3 respectively. Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60), osteosarcoma (MG-63) and breast carcinoma (MCF-7) cells : 15, 100 and 65, respectively. Elevation of serum calcium, serum osteocalcin, bone calcium and duodenal calbindin in rachitic chicks : all 1. (Ref. 0240)





By Sharpless kinetic epoxidation of the corresponding olefinic precursor. (Ref. 0243)



133
(23S,25R)-25-hydroxyvitamin D3 26,23-peroxylactone / (23S,25R)-25-hydroxycholecalciferol 26,23-peroxylactone
(5Z,7E)-(3S,23S,25R)-3,25-dihydroxy-9,10-seco-5,7,10(19)-cholestatrieno-26,23-peroxylactone
VVD0136
Sachiko Yamada
25R-OHD3 26,23S-peroxylactone
C27H40O5 444.604 Download ChemDraw structure file

lmax (nm) 264, lmin (nm) 228; spectrum (Ref. 0135)
1733 cm-1; spectrum(Ref. 0135)

m/z 444 (M+), 412 (M+-O2), 400 (M+-CO2), 372 (M+C3H4O2), 354 (372-H2O), 339 (354-CH3 and 372-OOH), 313 (M+C5H7O4), 271 (M+-side chain), 253 (M+-side chain-H2O), 136 (A ring+C6+C7)+, 118 (A ring+-H2O); spectrum(Ref. 0135)

HPLC: (Ref. 0135)
Isolated and identification : From the serum of rats given large doses of vitamin D3. (Ref. 0135)




134
(23R,25R)-1a,25-dihydroxyvitamin D3 26,23-lactone / (23R,25R)-1a,25-dihydroxycholecalciferol 26,23-lactone
(5Z,7E)-(1S,3R,23R,25R)-1,3,25-trihydroxy-9,10-seco-5,7,10(19)-cholestatrieno-26,23-lactone
VVD0137
Sachiko Yamada
1a,25R-(OH)2D3 26,23R-lactone
C27H40O5 444.604 Download ChemDraw structure file
Ability of the four diastereomers at C-23 and -25 of 1,25-(OH)2D3 26,23-lactone and 1,25-(OH)2D3 to bind to chick intestinal receptor was compared : Affinity relative to 1,25-(OH)2D3 : (23S,25S)-isomer, 8% ; (23R,25R)-isomer, 2% ; (23R,25S)-isomer, 0.2% ; (23S,25R)-isomer, 0.15%. (Ref. 0280)
Time-course response of 1,25-(OH)2D3 26,23-lactone four diastereomers in bone calcium mobilization induced in rats and dose-response of 1,25-(OH)2D3 26,23-lactone diastereomers in intestinal calcium transport and bone calcium mobilization. Figure (Ref. 0282)
1H-NMR (d, CDCl3, 400MHz) 6.38 (1H, d, J = 11.3 Hz, 6-H), 6.02 (1H, d, J = 11.3 Hz, 7-H), 5.33 (1H, m, 19-H), 5.01 (1H, m, 19-H), 4.77 (1H, m, 23-H), 4.43 (1H, m, 1b-H), 4.24 (1H, m, 3a-H), 1.52 (3H, s, 27-H), 1.03 (3H, d, J = 6.7 Hz, 21-H), 0.51 (3H, s, 18-H) (Ref. 0280)




Synthesis of four diastereomers at C-23 and -25 of the title compound from 1a-hydroxyergosterol. The stereochemistries at C-23 and -25 of the four diastereomers were determined by comparing their NMR spectra and HPLC properties with those of the four diastereomers at C-23 and -25 of 25-hydroxyvitamin D3 26,23-lactone. (Ref. 0280)



135
(23S,25R)-1a,25-dihydroxyvitamin D3 26,23-lactone / (23S,25R)-1a,25-dihydroxycholecalciferol 26,23-lactone
(5Z,7E)-(1S,3R,23S,25R)-1,3,25-trihydroxy-9,10-seco-5,7,10(19)-cholestatrieno-26,23-lactone
VVD0138
Sachiko Yamada
1a,25R-(OH)2D3 26,23S-lactone
C27H40O5 444.604 Download ChemDraw structure file
Affinity for the chick intestinal receptor: 1/662 as active as 1,25-(OH)2D3. In vitamin D deficient rats fed a low-calcium diet, this compound has a weak potency to increase intestinal calcium transport but it decrreases the serum calcium level: 500 ng dose decreases the serum calcium level by about 20% at 24 h. (Ref. 0242)
Ability of the four diastereomers at C-23 and -25 of 1,25-(OH)2D3 26,23-lactone and 1,25-(OH)2D3 to bind to chick intestinal receptor was compared: Affinity relative to 1,25-(OH)2D3: (23S,25S)-isomer, 7.9% ; (23R,25R)-isomer, 2.3%; (23R,25S)-isomer, 0.22%; (23S,25R)-isomer, 0.17%. (Ref. 0280)
Time-course response of 1,25-(OH)2D3 26,23-lactone four diastereomers in bone calcium mobilization induced in rats. Dose-response of 1,25-(OH)2D3 26,23-lactone diastereomers in intestinal calcium transport and bone calcium mobilization. (Ref. 0282)
[a]d-25 +21.3 degC (c = 0.47 in Et2O) [Lit. [a]D +24.66 degC (in Et2O)] (Ref. 0078/0280)
(95% EtOH) lmax (nm) 264, lmin (nm) 228 (Ref. 0078/0280)
(KBr) 3416, 2940, 1771, 1212, 1054 cm-1 (Ref. 0078/0280)
1H-NMR (d, CDCl3) 0.55 (3H, s, 18-H), 1.03 (3H, d, J = 5.9 Hz, 21-H), 1.48 (3H, s, 27-H), 4.22 (1H, m, 3-H), 4.44 (2H, m, 1- and 23-H), 5.00 and 5.33 (each 1H, m, 19-H), 6.02 and 6.38 (each 1H, d, J = 11 Hz, 7- and 6-H, respectively) (Ref. 0078/0280)
1H-NMR (d, CD3OD) 0.59 (3H, s, 18-H), 1.05 (3H, d, J = 6.4 Hz, 21-H), 1.44 (3H, s, 27-H), 4.14 (1H, m, 3-H), 4.36 (1H, m, 1-H), 4.49 (1H, m, 23-H), 4.91 and 5.29 (each 1H, m, 19-H), 6.09 and 6.33 (each 1H, d, J = 11 Hz, 7- and 6-H, respectively) (Ref. 0078/0280)
m/z 444 (M+, 6), 426 (13), 408 (14), 269 (7), 251 (16), 134 (100) (Ref. 0078/0280)


In normal beagle dogs, serum concentrations of 1,25R-(OH)2D3 26,23S-lactone, 1,25-(OH)2D3 and 1,24,25-(OH)3D3 were 100, 36, and 6 pg/ml serum. (Ref. 0085)
From 1a-hydroxydehydroepiandrosterone: The side chain was introduced via the reaction of C(22)-aldehyde with chiral C(5)-sulfone having the desired stereochemistry at C(25) of the target compound as key step. The lactone structure was constructed stereoselectively by iodolactonization of 22-ene-25-carboxylic acid. Provitamin D with the required side chain was converted to the title compound by photochemical method. (Ref. 0078)
Synthesis of four diastereomers at C-23 and -25 of the title compound from 1a-hydroxyergosterol and determination of the stereochemistry of the natural metabolite to be (23S, 25R). The stereochemistries at C-23 and -25 of the four diastereomers were determined by comparing their NMR spectra and HPLC properties with those of the four diastereomers at C-23 and -25 of 25-hydroxyvitamin D3 26,23-lactone (Ref. 0280)
The role of kidney in the production of 25-OHD3 26,23-lactone and 1,25-(OH)2D3 26,23-lactone was demonstrated. (Ref. 0120)


136
(23R,25S)-1a,25-dihydroxyvitamin D3 26,23-lactone / (23R,25S)-1a,25-dihydroxycholecalciferol 26,23-lactone
(5Z,7E)-(1S,3R,23R,25S)-1,3,25-trihydroxy-9,10-seco-5,7,10(19)-cholestatrieno-26,23-lactone
VVD0139
Sachiko Yamada
1a,25S-(OH)2D3 26,23R-lactone
C27H40O5 444.604 Download ChemDraw structure file
Ability of the four diastereomers at C-23 and -25 of 1,25-(OH)2D3 26,23-lactone and 1,25-(OH)2D3 to bind to chick intestinal receptor was compared : Affinity relative to 1,25-(OH)2D3 : (23S,25S)-isomer, 8% ; (23R,25R)-isomer, 2% ; (23R,25S)-isomer, 0.2% ; (23S,25R)-isomer, 0.15%. (Ref. 0280)
Time-course response of 1,25-(OH)2D3 26,23-lactone four diastereomers in bone calcium mobilization induced in rats and dose-response of 1,25-(OH)2D3 26,23-lactone diastereomers in intestinal calcium transport and bone calcium mobilization. Figure (Ref. 0282)
1H-NMR (d, CDCl3, 400MHz) 6.37 (1H, d, J = 11.3 Hz, 6-H), 6.02 (1H, d, J = 11.3 Hz, 7-H), 5.34 (1H, m, 19-H), 5.00 (1H, m, 19-H), 4.46 (2H, m, 23- and 1b-H), 4.24 (1H, m, 3a-H), 1.50 (3H, s, 27-H), 1.01 (3H, d, J = 6.4 Hz, 21-H), 0.57 (3H, s, 18-H) (Ref. 0280)




Synthesis of four diastereomers at C-23 and -25 of the title compound from 1a-hydroxyergosterol. The stereochemistries at C-23 and -25 of the four diastereomers were determined by comparing their NMR spectra and HPLC properties with those of the four diastereomers at C-23 and -25 of 25-hydroxyvitamin D3 26,23-lactone. (Ref. 0280)



137
(23S,25S)-1a,25-dihydroxyvitamin D3 26,23-lactone / (23S,25S)-1a,25-dihydroxycholecalciferol 26,23-lactone
(5Z,7E)-(1S,3R,23S,25S)-1,3,25-trihydroxy-9,10-seco-5,7,10(19)-cholestatrieno-26,23-lactone
VVD0140
Sachiko Yamada
1a,25S-(OH)2D3 26,23S-lactone
C27H40O5 444.604 Download ChemDraw structure file
Ability of the four diastereomers at C-23 and -25 of 1,25-(OH)2D3 26,23-lactone and 1,25-(OH)2D3 to bind to chick intestinal receptor was compared: Affinity relative to 1,25-(OH)2D3 : (23S,25S)-isomer, 8% ; (23R,25R)-isomer, 2% ; (23R,25S)-isomer, 0.2% ; (23S,25R)-isomer, 0.15%. (Ref. 0280)
Time-course response of 1,25-(OH)2D3 26,23-lactone four diastereomers in bone calcium mobilization induced in rats and dose-response of 1,25-(OH)2D3 26,23-lactone diastereomers in intestinal calcium transport and bone calcium mobilization. Figure (Ref. 0282)
1H-NMR (d, CDCl3, 400MHz) 6.38 (1H, d, J = 11.3 Hz, 6-H), 6.01 (1H, d, J = 11.3 Hz, 7-H), 5.33 (1H, m, 19-H), 5.00 (1H, m, 19-H), 4.72 (1H, m, 23-H), 4.33 (1H, m, 1b-H), 4.23 (1H, m, 3a-H), 1.51 (3H, s, 27-H), 1.03 (3H, d, J = 6.4 Hz, 21-H), 0.56 (3H, s, 18-H) (Ref. 0280)




Synthesis of four diastereomers at C-23 and -25 of the title compound from 1a-hydroxyergosterol. The stereochemistries at C-23 and -25 of the four diastereomers were determined by comparing their NMR spectra and HPLC properties with those of the four diastereomers at C-23 and -25 of 25-hydroxyvitamin D3 26,23-lactone. (Ref. 0280)



138
(25R)-26,26,26-trideuterio-1a,25-dihydroxyvitamin D3 / (25R)-26,26,26-trideuterio-1a,25-dihydroxycholecalciferol
(5Z,7E)-(1S,3R,25R)-26,26,26-trideuterio-9,10-seco-5,7,10(19)-cholestatriene-1,25-diol
VVD0141
Sachiko Yamada
1a,25R-(OH)2-[26,26,26-2H]D3
C27H41D3O3 419.613 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for rat intestinal receptor : 83 ; Calf intestinal receptor : 97 ; Intestinal calcium absorption, 136 ; Bone calcium mobilization, 143. (Ref. 0329)





Total convergent synthesis via Wittig-Horner coupling of upper half 8-ketone with A ring phosphine oxide. The upper half was synthesized from CD-ring 23-nitrone via 1,3-dipolar cycloaddition with methyl methacrylate as key step. (Ref. 0329)



139
(25S)-26,26,26-trideuterio-1a,25-dihydroxyvitamin D3 / (25S)-26,26,26-trideuterio-1a,25-dihydroxycholecalciferol
(5Z,7E)-(1S,3R,25S)-26,26,26-trideuterio-9,10-seco-5,7,10(19)-cholestatriene-1,25-diol
VVD0142
Sachiko Yamada
1a,25S-(OH)2-[26,26,26-2H]D3
C27H41D3O3 419.613 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for rat intestinal receptor : 148 ; Calf intestinal receptor : 161 ; Intestinal calcium absorption, 92 ; Bone calcium mobilization, 149. (Ref. 0329)





Total convergent synthesis via Wittig-Horner coupling of upper half 8-ketone with A ring phosphine oxide. The upper half was synthesized from CD-ring 23-nitrone via 1,3-dipolar cycloaddition with methyl methacrylate as key step. (Ref. 0329)



140
(24R)-24,25-dihydroxy-[6,19,19-2H3]vitamin D3 / (24R)-24,25-dihydroxy-[6,19,19-2H3]cholecalciferol
(5Z,7E)-(3S,24R)-[6,19,19-2H3]-9,10-seco-5,7,10(19)-cholestatriene-3,24,25-triol
VVD0143
Sachiko Yamada
24R,25-(OH)2-[6,19,19-2H3]D3
C27H41D3O3 419.613 Download ChemDraw structure file

(EtOH) lmax (nm) 265 (Ref. 0332)
(KBr) 3450, 2970, 2900, 1640, 1630, 1450, 1380, 1162, 1075, 965 cm-1 (Ref. 0332)
1H-NMR (d, CDCl3) 0.55 (3H, s, 18-H), 0.94 (3H, d, J = 5.0 Hz, 21-H), 1.17 and 1.22 (each 3H, s, 26- and 27-H), 3.31 (1H, m, 24-H), 3.93 (1H, m, 3-H), 6.02 (1H, s, 7-H) (Ref. 0332)




From 24R,25-dihydroxyvitamin D3 via proton-deuterium exchange at 6 and 19-positions of its sulfur dioxide adduct under basic conditions. (Ref. 0332)



141
(5E)-(24R)-24,25-dihydroxy-[6,19,19-2H3]vitamin D3 / (5E)-(24R)-24,25-dihydroxy-[6,19,19-2H3]cholecalciferol
(5E,7E)-(3S,24R)-[6,19,19-2H3]-9,10-seco-5,7,10(19)-cholestatriene-3,24,25-triol
VVD0144
Sachiko Yamada
(5E)-24R,25-(OH)2-[6,19,19-2H3]D3
C27H41D3O3 419.613 Download ChemDraw structure file

(EtOH) lmax (nm) 273 (Ref. 0332)
(KBr) 3650, 3450, 3020, 2950, 1210, 1060 cm-1 (Ref. 0332)
1H-NMR (d, CDCl3) 0.57 (3H, s, 18-H), 0.95 (3H, d, J = 5.0 Hz, 21-H), 1.17 and 1.22 (each 3H, s, 26- and 27-H), 3.32 (1H, m, 24-H), 3.84 (1H, m, 3-H), 5.86 (1H, s, 7-H) (Ref. 0332)
m/z 419 (M+, 83), 401 (30), 274 (67), 256 (68), 160 (68), 139 (70), 121 (100) (Ref. 0332)



From 24R,25-dihydroxyvitamin D3 via proton-deuterium exchange at 6 and 19-positions of its sulfur dioxide adduct under basic conditions. (Ref. 0332)



142
(20R,24R)-20-fluoro-1a,24-dihydroxy-26,27-cyclovitamin D3 / (20R,24R)-20-fluoro-1a,24-dihydroxy-26,27-cyclocholecalciferol
(5Z,7E)-(1S,3R,20R,24R)-20-fluoro-26,27-cyclo-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0145
Sachiko Yamada
20R-F-1a,24R-(OH)2-26,27-cyclo-D3
C27H41FO3 432.611 Download ChemDraw structure file

(KBr) 3400, 2900 cm-1 (Ref. 0161)
1H-NMR (d, CDCl3, 300MHz) 6.02 and 6.39 (1H each, 2 times d, J = 11 Hz, 6- and 7-H), 5.00 and 5.34 (1H each, 2 times s, 19-H), 4.43 (1H, m, 1-H), 4.22 (1H, m, 3-H), 2.88 (1H, m, 24-H), 1.30 (3H, d, J = 20 Hz, 21-H), 0.90 (1H, m, 25-H), 0.70 (3H, d, J = 3 Hz, 18-H), 0.54 and 0.28 (2H each, 2 times m, 26- and 27-H) (Ref. 0161)
m/z 432 (M+, 9%),414 (10%), 394 (10%), 376 (7%), 358 (3%), 134 (100%) (Ref. 0161)



Synthesis of the four diastereomers at C(20) and C(24) from protected (5E)-1a-hydroxy-22-oxo-23,24,25,26,27-pentanorvitamin D3 via fluorination of its silylenol ether and introduction of the side chain fragment by Wittig type reaction as key steps. (Ref. 0161)



143
(20S,24R)-20-fluoro-1a,24-dihydroxy-26,27-cyclovitamin D3 / (20S,24R)-20-fluoro-1a,24-dihydroxy-26,27-cyclocholecalciferol
(5Z,7E)-(1S,3R,20S,24R)-20-fluoro-26,27-cyclo-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0146
Sachiko Yamada
20S-F-1a,24R-(OH)2-26,27-cyclo-D3
C27H41FO3 432.611 Download ChemDraw structure file

(KBr) 3400, 2930 cm-1 (Ref. 0161)
1H-NMR (d, CDCl3, 300MHz) 6.02 and 6.39 (1H each, 2 times d, J = 11 Hz, 6- and 7-H), 5.00 and 5.33 (1H each, 2 times s, 19-H), 4.43 (1H, m, 1-H), 4.22 (1H, m, 3-H), 2.85 (1H, m, 24-H), 1.41 (3H, d, J = 21 Hz, 21-H), 0.70 (3H, d, J = 4 Hz, 18-H) (Ref. 0161)
m/z 432 (M+, 7%),414 (10%), 394 (8%), 376 (7%), 152 (34%), 134 (100%) (Ref. 0161)



Synthesis of the four diastereomers at C(20) and C(24) from protected (5E)-1a-hydroxy-22-oxo-23,24,25,26,27-pentanorvitamin D3 via fluorination of its silylenol ether and introduction of the side chain fragment by Wittig type reaction as key steps. (Ref. 0161)



144
(20R,24S)-20-fluoro-1a,24-dihydroxy-26,27-cyclovitamin D3 / (20R,24S)-20-fluoro-1a,24-dihydroxy-26,27-cyclocholecalciferol
(5Z,7E)-(1S,3R,20R,24S)-20-fluoro-26,27-cyclo-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0147
Sachiko Yamada
20R-F-1a,24S-(OH)2-26,27-cyclo-D3
C27H41FO3 432.611 Download ChemDraw structure file

(KBr) 3400, 2900 cm-1 (Ref. 0161)
1H-NMR (d, CDCl3, 300MHz) 6.02 and 6.39 (1H each, 2 times d, J = 11 Hz, 6- and 7-H), 5.01 and 5.34 (1H each, 2 times s, 19-H), 4.43 (1H, m, 1-H), 4.22 (1H, m, 3-H), 2.85 (1H, m, 24-H), 1.30 (3H, d, J = 20 Hz, 21-H), 0.90 (1H, m, 25-H), 0.70 (3H, d, J = 3 Hz, 18-H), 0.53 and 0.27 (2H each, 2 times m, 26- and 27-H) (Ref. 0161)
m/z 432 (M+, 8%),414 (13%), 394 (14%), 376 (8%), 358 (3%), 134 (100%) (Ref. 0161)



Synthesis of the four diastereomers at C(20) and C(24) from protected (5E)-1a-hydroxy-22-oxo-23,24,25,26,27-pentanorvitamin D3 via fluorination of its silylenol ether and introduction of the side chain fragment by Wittig type reaction as key steps. (Ref. 0161)



145
(20S,24S)-20-fluoro-1a,24-dihydroxy-26,27-cyclovitamin D3 / (20S,24S)-20-fluoro-1a,24-dihydroxy-26,27-cyclocholecalciferol
(5Z,7E)-(1S,3R,20S,24S)-20-fluoro-26,27-cyclo-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0148
Sachiko Yamada
20S-F-1a,24S-(OH)2-26,27-cyclo-D3
C27H41FO3 432.611 Download ChemDraw structure file

(KBr) 3400, 2920 cm-1 (Ref. 0161)
1H-NMR (d, CDCl3, 300MHz) 6.02 and 6.39 (1H each, 2 times d, J = 11 Hz, 6- and 7-H), 5.00 and 5.33 (1H each, 2 times s, 19-H), 4.43 (1H, m, 1-H), 4.22 (1H, m, 3-H), 2.85 (1H, m, 24-H), 1.41 (3H, d, J = 21 Hz, 21-H), 0.70 (3H, d, J = 4 Hz, 18-H) (Ref. 0161)
m/z 432 (M+, 8%),414 (13%), 394 (12%), 376 (9%), 152 (33%), 134 (100%) (Ref. 0161)



Synthesis of the four diastereomers at C(20) and C(24) from protected (5E)-1a-hydroxy-22-oxo-23,24,25,26,27-pentanorvitamin D3 via fluorination of its silylenol ether and introduction of the side chain fragment by Wittig type reaction as key steps. (Ref. 0161)



146
26,26,26-trifluoro-25-hydroxyvitamin D3 / 26,26,26-trifluoro-25-hydroxycholecalciferol
(5Z,7E)-(3S)-26,26,26-trifluoro-9,10-seco-5,7,10(19)-cholestatriene-3,25-diol
VVD0149
Sachiko Yamada
26,26,26-F3-25-OHD3
C27H41F3O2 454.608 Download ChemDraw structure file

lmax (nm) 265, lmin (nm) 227 (Ref. 0201)

m/z 454 (M+), 493, 436, 421, 271, 253, 136, 118 (Ref. 0201)



From 24-phenylsulfonyl-5-cholen-3-ol via reaction with trifluoroacetate as a key step. (Ref. 0201)



147
(25R)-26,26,26-trifluoro-1a,25-dihydroxyvitamin D3 / (25R)-26,26,26-trifluoro-1a,25-dihydroxycholecalciferol
(5Z,7E)-(1S,3R,25R)-26,26,26-trifluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0150
Sachiko Yamada
26,26,26-F3-1a,25R-(OH)2D3
C27H41F3O3 470.608 Download ChemDraw structure file
Potency relative to 1,25-(OH)2D3 (defined 1): Differentiation of HL-60 cells: 3; Calcemic activity: 2. (Ref. 0356)









148
(25S)-26,26,26-trifluoro-1a,25-dihydroxyvitamin D3 / (25S)-26,26,26-trifluoro-1a,25-dihydroxycholecalciferol
(5Z,7E)-(1S,3R,25S)-26,26,26-trifluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0151
Sachiko Yamada
26,26,26-F3-1a,25S-(OH)2D3
C27H41F3O3 470.608 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Intestinal calcium absorption in rat, 197 ; Bone calcium mobilization in rat, 163 ; Competitive binding to rat intestinal vitamin D receptor, 199 ; Differentiation of human leukemia cells (HL-60), 300. (Ref. 0237)









149
4,4-difluorovitamin D3 / 4,4-difluorocholecalciferol
(5E,7E)-(3S)-4,4-difluoro-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0152
Sachiko Yamada
4,4-F2-D3
C27H42F2O 420.619 Download ChemDraw structure file

(95% EtOH) lmax (nm) (emax) 270 (19400) (Ref. 0333)
1H-NMR (d, CDCl3) 0.55 (3H, s, 18-H), 0.86 and 0.87 (each 3H, d, J = 6.6 Hz, 26- and 27-H), 0.92 (3H, d, J = 6.2 Hz, 21-H), 2.19 (1H, m, 1-H), 2.47 (1H, m, 1-H), 3.98 (1H, m, 3-H), 5.00 and 5.23 (each 1H, s, 19-H), 6.09 (1H, d, J = 11.4 Hz, 7-H), 6.94 (1H, d, J = 11.4 Hz, 6-H) (Ref. 0333)
19F-NMR (d, CDCl3) -114.0 (dd, J = 234.6 and 11.5 Hz, 4b-F), -108.0 (d, J = 234.6 Hz, 4a-F) (Ref. 0333)
m/z 420 (M+, 93), 382 (79), 380 (18), 335 (22), 307 (61), 269 (33), 267 (16), 135 (100) (Ref. 0333)



From 4,7-cholestadien-3-one via electrophilic difluorination at C(4) followed by reduction giving 4,4-difluoroprovitamin D3 as a key step. (Ref. 0345)



150
(5Z)-4,4-difluorovitamin D3 / (5Z)-4,4-difluorocholecalciferol
(5Z,7E)-(3S)-4,4-difluoro-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0153
Sachiko Yamada
(5Z)-4,4-F2-D3
C27H42F2O 420.619 Download ChemDraw structure file

(95% EtOH) lmax (nm) (emax) 277 (23000) (Ref. 0333)
1H-NMR (d, CD3OD) 0.60 (3H, s, 18-H), 0.89 (6H, d, J = 6.6 Hz, 26- and 27-H), 0.96 (3H, d, J = 6.1 Hz, 21-H), 2.23 (1H, m, 1-H), 2.52 (1H, m, 1-H), 3.88 (1H, m, 3-H), 4.82 and 5.01 (each 1H, s, 19-H), 6.40 (1H, d, J = 12.0 Hz, 7-H), 6.83 (1H, d, J = 12.0 Hz, 6-H) (Ref. 0333)
19F-NMR (d, CDCl3) -109.0 (d, J = 248.7 Hz), -101.7 (d, J = 248.7 Hz) (Ref. 0333)




From 4,7-cholestadien-3-one via electrophilic difluorination at C(4) followed by reduction giving 4,4-difluoroprovitamin D3 as a key step. (Ref. 0345)



151
1a,25-difluorovitamin D3 / 1a,25-difluorocholecalciferol
(5Z,7E)-(1S,3R)-1,25-difluoro-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0154
Sachiko Yamada
1a,25-F2-D3
C27H42F2O 420.619 Download ChemDraw structure file
The title compound showed no response in intestinal calcium transport and elevation of serum calcium level in vitamin D deficient rats. Antivitamin D properties of the title compound was tested. At a 1000-fold excess administration, this compound failed to block the expression of vitamin D activity. (Stereochemistry at C-1 is ambiguous) (Ref. 0296)
lmax (nm) 265 (Ref. 0296)
1H-NMR (d) 0.53 (3H, s, 18-CH3), 0.93 (3H, d, J = 6.0 Hz, 21-CH3), 1.34 (6H, d, J = 22.0 Hz, 26- and 27-CH3), 3.98 (1H, m, 3-H), 5.02 (1H, d m, J = 52.0 Hz, 1-H), 5.12 [1H, m(sharp), 19(Z)-H], 5.41 [1H, m(sharp), 19(E)-H], 6.03 (1H, d, J = 11.0 Hz, 7-H), 6.44 (1H, d, J = 11.0 Hz, 6-H) (Ref. 0296)
m/z 420 (M+, 20), 400 (70), 382 (35), 135 (100) (Ref. 0296)



From 1a,25-(OH)2D3 3-acetate, by fluorination with diethylaminosulfurtrifluoride followed by deprotection. (Stereochemistry at C-1 is ambiguous) (Ref. 0296)



152
24,24-difluoro-1a-hydroxyvitamin D3 / 24,24-difluoro-1a-hydroxycholecalciferol
(5Z,7E)-(1S,3R)-24,24-difluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0155
Sachiko Yamada
24,24-F2-1a-OH-D3
C27H42F2O2 436.618 Download ChemDraw structure file
The analogue showed higher activity than 24,24-difluoro-1a,25-dihydroxyvitamin D3 in intestinal calcium absorption. (Ref. 0251)
[a]D +75.6 deg (c = 0.15 in CHCl3) (Ref. 0251)
(EtOH) lmax (nm) (e) 264 (18100) (Ref. 0251)
(neat) 3422, 1645, 1456 cm-1 (Ref. 0251)
1H-NMR (d, CDCl3, 400MHz) 0.55 (3H, s), 0.94 (3H, d, J = 6.4 Hz), 1.00 (6H, d, J = 7.0 Hz), 4.20-4.25 (1H, m), 4.43 (1H, dd, J = 4.6, 7.6 Hz), 5.00 (1H, s), 5.33 (1H, t, J = 1.7 Hz), 6.02 (1H, d, J = 11.5 Hz), 6.38 (1H, d, J = 11.5 Hz) (Ref. 0251)
m/z 436 (M+), 418 (M+-H2O), 400 (M+-2H2O), 152, 134 (Ref. 0251)

HPLC : Lichrosorb Si-60, 25 times 250 mm ; mobile phase, 8 % isoPrOH-CH2Cl2 (Ref. 0251)

The PTAD adduct of 1a,3b-bis[(tert-butyldimethylsilyl)oxy]-24-norchol-5,7-dien-23-al was modified to give the analogues with fluorine atoms in the side-chain. The radical deoxygenation of the 25-OH was a key feature in the synthesis. (Ref. 0251)



153
4,4-difluoro-1a-hydroxyvitamin D3 / 4,4-difluoro-1a-hydroxycholecalciferol
(5E,7E)-(1S,3S)-4,4-difluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0156
Sachiko Yamada
4,4-F2-25-OHD3
C27H42F2O2 436.618 Download ChemDraw structure file

(95% EtOH) lmax (nm) 271 (Ref. 0333)
1H-NMR (d, CDCl3) 0.55 (3H, s, H-18), 0.86 and 0.87 (each 3H, d, J = 6.6 Hz, H-26 and 27), 0.92 (3H, d, J = 6.2 Hz, H-21), 2.08 (2H, m, H-2), 2.90 (1H, m, H-9), 4.26 (1H, m, H-3), 4.49 (1H, t, J = 5.6 Hz, H-1), 5.18 and 5.50 (each 1H, s, H-19), 6.07 (1H, d, J = 11.4 Hz, H-7), 7.06 (1H, d, J = 11.4 Hz, H-6) (Ref. 0333)
19F-NMR (d, CDCl3) -116.3 (d, J = 237.9 Hz, 4b-F), -107.7 (br d, J = 237.9 Hz, 4a-F) (Ref. 0333)
m/z 436 (M+, 54), 418 (6), 398 (9), 380 (6), 351 (25), 323 (58), 305 (12), 285 (6), 259 (11), 135 (100) (Ref. 0333)



From 4,7-cholestadien-3-one via electrophilic difluorination at C(4) followed by reduction giving 4,4-difluoroprovitamin D3 as a key step. (Ref. 0345)



154
(5Z)-4,4-difluoro-1a--hydroxyvitamin D3 / (5Z)-4,4-difluoro-1a--hydroxycholecalciferol
(5Z,7E)-(1S,3S)-4,4-difluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0157
Sachiko Yamada
(5Z)-4,4-F2-25-OHD3
C27H42F2O2 436.618 Download ChemDraw structure file






From 4,7-cholestadien-3-one via electrophilic difluorination at C(4) followed by reduction giving 4,4-difluoroprovitamin D3 as a key step. (Ref. 0345)



155
23,23-difluoro-25-hydroxyvitamin D3 / 23,23-difluoro-25-hydroxycholecalciferol
(5Z,7E)-(3S)-23,23-difluoro-9,10-seco-5,7,10(19)-cholestatriene-3,25-diol
VVD0158
Sachiko Yamada
23,23-F2-25-OHD3
C27H42F2O2 436.618 Download ChemDraw structure file
The title compound is 5-10 times less active than 25-OHD3 in stimulating intestinal calcium transport, bone calcium mobilization, increasing serum phosphorus, mineralization of rachitic bone, and binding to the plasma transport protein in rats. (Ref. 0301)
(EtOH) lmax (nm) 265, lmin (nm) 228 (Ref. 0202)
1H-NMR (d, CDCl3) 0.58 (3H, s, 18-H3), 1.07 (3H, d, J = 6.1 Hz, 21-H3), 1.34 (6H, s, 26- and 27-H3), 3.95 (1H, m, 3-H), 4.81 (1H, bs, 19-H), 5.04 (1H, bs, 19-H), 6.03 (1H, d, J = 10.7 Hz, 7-H), 6.23 (1H, J = 10.7 Hz, 6-H) (Ref. 0202)
m/z 436 (M+), 418, 403 (Ref. 0202)



From 6b-methoxy-3a,5-cyclo-23,24-dinor-5a-cholan-22-ol via methyl 23,23-difluoro-cholan-24-oate. as key intermediate. (Ref. 0202)



156
24,24-difluoro-25-hydroxyvitamin D3 / 24,24-difluoro-25-hydroxycholecalciferol
(5Z,7E)-(3S)-24,24-difluoro-9,10-seco-5,7,10(19)-cholestatriene-3,25-diol
VVD0159
Sachiko Yamada
24,24-F2-25-OHD3
C27H42F2O2 436.618 Download ChemDraw structure file

(95% EtOH) lmax (nm) (logemax) 265 (4.24) (Ref. 0303)
1H-NMR (d, CDCl3) 0.56 (3 H, s), 0.95 (3 H, d, J = 6 Hz), 1.32 (6 H, s), 3.95 (1 H, m, W/2 = 20 Hz), 4.85 (1 H, bs), 5.08 (1 H, bs), 6.16 (2 H, AB type q, J = 11 Hz) (Ref. 0303)
m/z 436 (M+), 421, 418, 403, 377, 271, 253, 136, 118 (Ref. 0199)



From lithocholic acid via fluorination of 24-oxo-25-carboxylic acid ester with DAST (diethylaminosulfur trifluoride) as a key step to construct the desired side chain structure. (Ref. 0303)



157
4,4-difluoro-1a,25-dihydroxyvitamin D3 / 4,4-difluoro-1a,25-dihydroxycholecalciferol
(5E,7E)-(1S,3S)-4,4-difluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0160
Sachiko Yamada
4,4-F2-1a,25-(OH)2D3
C27H42F2O3 452.617 Download ChemDraw structure file

(95% EtOH) lmax (nm) 271 (Ref. 0333)
1H-NMR (d, CDCl3) 0.55 (3H, s, 18-H), 0.94 (3H, d, J = 6.4 Hz, 21-H), 1.22 (6H, s, 26- and 27-H), 2.09 (2H, m, 2-H), 2.90 (1H, m, 9-H), 4.25 (1H, m, 3-H), 4.49 (1H, t, J = 5.6 Hz, 1-H), 5.18 and 5.50 (each 1H, s, 19-H), 6.07 (1H, d, J = 11.5 Hz, 7-H), 7.06 (1H, d, J = 11.5 Hz, 6-H) (Ref. 0333)
19F-NMR (d, CDCl3) -116.3 (d, J = 237.0 Hz, 4b-F), -107.6 (br d, J = 237.0 Hz, 4a-F) (Ref. 0333)
m/z 452 (M+, 17), 434 (34), 419 (12), 414 (10), 396 (10), 351 (13), 323 (56), 305 (18), 303 (11), 285 (12), 135 (100) (Ref. 0333)



From 25-hydroxy-4,7-cholestadien-3-one via electrophilic difluorination at C(4) followed by reduction giving 4,4-difluoro-25-hydroxyprovitamin D3 as a key step. (Ref. 0333)



158
(5Z)-4,4-difluoro-1a,25-dihydroxyvitamin D3 / (5Z)-4,4-difluoro-1a,25-dihydroxycholecalciferol
(5Z,7E)-(1S,3S)-4,4-difluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0161
Sachiko Yamada
(5Z)-4,4-F2-1a,25-(OH)2D3
C27H42F2O3 452.617 Download ChemDraw structure file






From 25-hydroxy-4,7-cholestadien-3-one via electrophilic difluorination at C(4) followed by reduction giving 4,4-difluoro-25-hydroxyprovitamin D3 as a key step. (Ref. 0333)



159
23,23-difluoro-1a,25-dihydroxyvitamin D3 / 23,23-difluoro-1a,25-dihydroxycholecalciferol
(5Z,7E)-(1S,3R)-23,23-difluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0162
Sachiko Yamada
23,23-F2-1a,25-(OH)2D3
C27H42F2O3 452.617 Download ChemDraw structure file
Affinity for chick intestinal receptor : 1/7 as active as 1,25-(OH)2D3 ; Intestinal calcium transport, approximately as potent as 1,25-(OH)2D3. (Ref. 0301)

m/z 452 (M+), 434, 416, 287, 269, 251, 152, 134 (Ref. 0301)



From 23,23-difluoro-25-hydroxyvitamin D3 by in vitro incubation with vitamin D-deficient chick kidney homogenates and subsequent purification on three HPLC systems. (Ref. 0301)



160
24,24-difluoro-1a,25-dihydroxyvitamin D3 / 24,24-difluoro-1a,25-dihydroxycholecalciferol
(5Z,7E)-(1S,3R)-24,24-difluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0163
Sachiko Yamada
24,24-F2-1a,25-(OH)2D3
C27H42F2O3 452.617 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Intestinal calcium absorption in rat, 235 ; Bone calcium mobilization in rat, 58 ; Competitive binding to rat intestinal vitamin D receptor, 229 ; Differentiation of human leukemia cells (HL-60), 1000. (Ref. 0237)
The analogue was about four to five times more active than 1a,25-dihydroxyvitamin D3 to stimulate the chick intestinal calcium uptake. (Ref. 0253)
The analogue, 24,24-F2-1a,25-(OH)2D3 was four to seven times more potent than 1a,25-(OH)2D3 in inducing phagocytosis and C3 rosette formation of HL-60 cells. (Ref. 0254)
The analogue induced macrophage differentiation of leukemic myeloid colony-forming cells, and the potency of the induction by 1a,25-(OH)2D3 and 24,24-F2-1a,25-(OH)2D3 was almost equivalent. (Ref. 0255)
The analogue induced a significantly greater hypercalcemia and hyperphophatemia than did 1a,25-(OH)2D3. (Ref. 0256)
[a]D +10.0 deg (c = 0.25 in EtOH) (Ref. 0258)
lmax (nm) (emax) 265 (18100) (Ref. 0258)
(CHCl3) 3690 cm-1 (Ref. 0258)
1H-NMR (d, CDCl3, 400MHz) 0.55 (3H, s), 0.95 (3H, d, J = 6.4 Hz), 1.30-2.14 (3H, m), 1.31 (6H, s), 2.31 (1H, dd, J = 6.4, 13.1 Hz), 2.60 (1H, dd, J = 3.4, 13 Hz), 2.83 (1H, dd, J = 3.5, 12 Hz), 4.23 (1H, tt, J = 3.2, 6.4 Hz), 4.43 (1H, dd, J = 4.3, 7.3 Hz), 5.33 (1H, t, J = 1.5 Hz), 6.02 (1H, d, J = 11.3 Hz), 6.38 (1H, d, J = 11.3 Hz) (Ref. 0258)
m/z 452 (M+), 434 (M+-H2O), 416 (M+-2H2O) (Ref. 0258)



The analogue was synthesized from 24,24-difluoro-5b-chorestane-3a,25-diol, which was prepared from lithocholic acid in 20 % overall yield. (Ref. 0252)
Synthesis was accomplished from vitamin D2 via vitamin D2-SO2 adducts in 12.5 % overall yield in 11 steps. (Ref. 0257/0258)



161
(6RS)-6,19-epidioxy-24,24-difluoro-25-hydroxy-6,19-dihydrovitamin D3 / (6RS)-6,19-epidioxy-24,24-difluoro-25-hydroxy-6,19-dihydrocholecalciferol
(7E)-(3S, 6RS)-6,19-epidioxy-24,24-difluoro-9,10-seco-5(10),7-cholestadiene-3,25-diol
VVD0164
Sachiko Yamada
6,19-epidioxy-24,24-F2-25-OH-6,19-dihydro-D3
C27H42F2O4 468.617 Download ChemDraw structure file
Binding affinity for the vitamin D receptor in HL-60 cells : 1/1000 as active as 1,25-(OH)2D3. Differentiation of HL-60 cells : 1/45 as active as 1,25-(OH)2D3. (Ref. 0339)

m/z 468 (M+), 450, 330, 312, 299, 285, 258 (Ref. 0339)



As a major product by the reaction of 24,24-difluoro-25-hydroxyvitamin D3 with singlet oxygen generated by dye-sensitized photochemical method. (Ref. 0339)



162
24,25-didehydrovitamin D3 / 24,25-didehydrocholecalciferol
(5Z,7E)-(3S)-9,10-seco-5,7,10(19),24-cholestatetraen-3-ol
VVD0165
Sachiko Yamada
24,25-didehydro-D3 / 24-ene-D3
C27H42O 382.622 Download ChemDraw structure file










163
(22E)-1a-hydroxy-22,23-didehydrovitamin D3 / (22E)-1a-hydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R)-9,10-seco-5,7,10(19),22-cholestatetraene-1,3-diol
VVD0166
Sachiko Yamada
(22E)-1a-OH-22,23-didehydro-D3 / (22E)-1a-OH-22-ene-D3
C27H42O2 398.621 Download ChemDraw structure file
HL-60 human promyelocytes differentiation : ED50 in nitro blue tetrazplium reduction, phagocytic activity, and nonspecific acid esterase activity are 4.7 times 10-7 M, 6.0 times 10-7 M and 4.0 times 10-7 M, respectively, when 1,25-(OH)2D3 shows the respective ED50 values of 1.0 times 10-8 M, 1.0 times 10-8 M and 1.1 times 10-8 M, respectively. (Ref. 0228)





The side chain with 22E-stereochemistry was constructed with high selectivity by coupling of C(22) steroid aldehyde with isopentyl phenyl sulfone followed by reductive desulfonylation as a key step. 1a-Hydroxyl group was introduced by SeO2 oxidation of 3,5-cyclovitamin D after photochemical conversion to (22E)-22,23-didehydrovitamin D3. The 5Z isomer was obtained as a minor product in the cycloreversion of the 1a-hydroxylated cyclovitamin D. (Ref. 0244)



164
(22E)-1b-hydroxy-22,23-didehydrovitamin D3 / (22E)-1b-hydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1R,3R)-9,10-seco-5,7,10(19),22-cholestatetraene-1,3-diol
VVD0167
Sachiko Yamada
(22E)-1b-OH-22,23-didehydro-D3 / (22E)-1b-OH-22-ene-D3
C27H42O2 398.621 Download ChemDraw structure file






The side chain with 22E-stereochemistry was constructed with high selectivity by coupling of C(22) steroid aldehyde with isopentyl phenyl sulfone followed by reductive desulfonylation as a key step. The 1b-hydroxylated vitamin was obtained as a minor product in the SeO2 oxidation of 3,5-cyclo derivative of (22E)-22,23-didehydrovitamin D followed by cycloreversion. (Ref. 0244)



165
(22Z)-1a-hydroxy-22,23-didehydrovitamin D3 / (22Z)-1a-hydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22Z)-(1S,3R)-9,10-seco-5,7,10(19),22-cholestatetraene-1,3-diol
VVD0168
Sachiko Yamada
(22Z)-1a-OH-22,23-didehydro-D3 / (22Z)-1a-OH-22-ene-D3
C27H42O2 398.621 Download ChemDraw structure file






The side chain with 22Z-stereochemistry was constructed with high selectivity by coupling of C(22) steroid aldehyde with appropriate Wittig reagent. 1a-Hydroxyl group was introduced by SeO2 oxidation of 3,5-cyclovitamin D derivative after photochemical conversion to (22Z)-22,23-didehydrovitamin D3. The 5Z isomer was obtained as a minor product in the cycloreversion of the 1a-hydroxylated cyclovitamin D. (Ref. 0244)



166
(22Z)-1b-hydroxy-22,23-didehydrovitamin D3 / (22Z)-1b-hydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22Z)-(1R,3R)-9,10-seco-5,7,10(19),22-cholestatetraene-1,3-diol
VVD0169
Sachiko Yamada
(22Z)-1b-OH-22,23-didehydro-D3 / (22Z)-1b-OH-22-ene-D3
C27H42O2 398.621 Download ChemDraw structure file






The side chain with 22Z-stereochemistry was constructed with high selectivity by coupling of C(22) steroid aldehyde with appropriate Wittig reagent. The 1b-hydroxylated vitamin was obtained as a minor product in the SeO2 oxidation of 3,5-cyclo derivative of (22Z)-22,23-didehydrovitamin D followed by cycloreversion. (Ref. 0244)



167
(22Z)-1a-hydroxy-22,23-didehydrovitamin D3 / (22Z)-1a-hydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R)-9,10-seco-5,7,10(19),22-cholestatetraene-1,3-diol
VVD0170
Sachiko Yamada
(22Z)-1a-OH-22,23-didehydro-D3
C27H42O2 398.621 Download ChemDraw structure file
HL-60 human promyelocytes differentiation : ED50 in nitro blue tetrazplium reduction, phagocytic activity, and nonspecific acid esterase activity are all > 10-6 M, when 1,25-(OH)2D3 shows the respective ED50 values of 1.0 times 10-8 M, 1.0 times 10-8 M and 1.1 times 10-8 M, respectively. (Ref. 0228)









168
1a-hydroxy-24,25-didehydrovitamin D3 / 1a-hydroxy-24,25-didehydrocholecalciferol
(5Z,7E)-(1S,3R)-9,10-seco-5,7,10(19),24-cholestatetraene-1,3-diol
VVD0171
Sachiko Yamada
1a-OH-24,25-didehydro-D3 / 1a-OH-24-ene-D3
C27H42O2 398.621 Download ChemDraw structure file










169
1a,25-dihydroxy-9,11-didehydro-3-deoxyvitamin D3 / 1a,25-dihydroxy-9,11-didehydro-3-deoxycholecalciferol
(5Z,7E)-(1S)-9,10-seco-5,7,10(19),9(11)-cholestatetraene-1,25-diol
VVD0172
Sachiko Yamada
3-deoxy-1a,25-(OH)2-9,11-didehydro-D3
C27H42O2 398.621 Download ChemDraw structure file






From de-A,B-cholesta-9(11),25-dien-8-one and A-ring synthon (1-ethynyl-3-hydroxy-2-methyl-1-cyclohexene) via 9,10-seco-5(10),6,7,9(11),25- cholestapentaen-1-ol derivative as the key intermediate. (Ref. 0225)



170
25-hydroxy-16,17-didehydrovitamin D3 / 25-hydroxy-16,17-didehydrocholecalciferol
(5Z,7E)-(3S)-9,10-seco-5,7,10(19),16-cholestatetraene-3,25-diol
VVD0173
Sachiko Yamada
25-OH-16,17-didehydro-D3
C27H42O2 398.621 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 10 ; Competitive binding to rat intestinal vitamin D receptor, 0.23 ; Differentiation of human leukemia cells (HL-60), 3. (Ref. 0237)









171
23,24-didehydro-25-hydroxyvitamin D3 / 23,24-didehydro-25-hydroxycholecalciferol
(5Z,7E,23E)-(3S)-9,10-seco-5,7,10(19),23-cholestatetraene-3,25-diol
VVD0174
Sachiko Yamada
25-OH-23-dehydro-D3
C27H42O2 398.621 Download ChemDraw structure file


m/z 398 (11, M+), 380 (5, M+-H2O), 271 (2, M+-side chain), 253 (5, 271-H2O), 136 [100, (A ring+C6+C7)+], 118 (74, 136-H2O); spectrum (Ref. 0100)
bis-TMS-derivative : m/z 542 (22, M+), 527 (8, M+-CH3), 452 (18, M+HOSiMe3), 437 (8, 452-CH3), 208 [60, (A ring+C6+C7)+], 131 (56, C3H6OSiMe3+), 118 (100, 208-HOSiMe3); spectrum (Ref. 0100)


Isolated and identified from blood plasma of chicks given large doses of vitamin D3. (Ref. 0100)




172
calicoferol E
(8S)-3-hydroxy-9,10-seco-1,3,5(10)-cholestatrien-9-one
VVD0175
Sachiko Yamada
calicoferol E
C27H42O2 398.621 Download ChemDraw structure file

[a]D +21.6 deg (c = 0.6 in CHCl3) (Ref. 0316)
1H-NMR (d, CDCl3, 400MHz) 0.87 (6H, d, J = 6.5 Hz, 26-, 27-CH3), 0.93 (3H, d, J = 6.5 Hz, 21-CH3), 0.98 (3H, s, 18-CH3), 2.24 (3H, s, 19-CH3), 6.57 (1H, dd, J = 8.1, 2.7 Hz, 2-H), 6.67 (1H, d, J = 2.7 Hz, 4-H), 6.98 (1H, d, J = 8.1 Hz, 1-H) (Ref. 0316)
13C-NMR (d, CDCl3, 100MHz) 11.5, 18.4, 18.5, 22.5, 22.8, 23.8, 25.1, 27.6, 28.0, 29.0, 31.0, 35.6, 35.9, 38.3, 38.5, 39.4, 42.8, 50.4, 55.0, 55.2, 112.5, 115.7, 128.0, 131.0, 142.5, 153.7, 213.4 (Ref. 0316)
m/z 398 (M+), 277, 268, 264, 249, 223 (Ref. 0316)


Source see (Ref. 0319)
By the coupling of upper-half fragment derived from Grundmann



173
1-oxoprevitamin D3 / 1-oxoprecholecalciferol
(6Z)-(3R)-3-hydroxy-9,10-seco-5(10),6,8-cholestatriene-1-one
VVD0176
Sachiko Yamada
1-oxo-pre-D3
C27H42O2 398.621 Download ChemDraw structure file

(EtOH) lmax (nm) (emax) 288 (7100), 237 (6800) (Ref. 0176)
1H-NMR (d, CDCl3, 270MHz) 0.72 (3H, s, 13-Me), 1.80 (3H, s, 10-Me), 4.16 (1H, m, 3-H), 5.47 (1H, narrow m, 9-H), 6.14 and 6.03 (2H, AB q, J = 11.9 Hz, 6- and 7-H) (Ref. 0176)
m/z 398 (M+, 60%), 380 (100%), 365 (10%) (Ref. 0176)



From 1a-hydroxyvitamin D3 by selective (MnO2) oxidation of the allylic 1-hydroxyl group. (Ref. 0176)



174
1a-hydroxy-22-oxovitamin D3 / 1a-hydroxy-22-oxocholecalciferol
(5Z,7E)-(1S,3R)-1,3-dihydroxy-9,10-seco-5,7,10(19)-cholestatrien-22-one
VVD0177
Sachiko Yamada
1a-OH-22-oxo-D3
C27H42O3 414.621 Download ChemDraw structure file










175
24,25-epoxy-1a-hydroxyvitamin D3 / 24,25-epoxy-1a-hydroxycholecalciferol
(5Z,7E)-(1S,3R)-24,25-epoxy-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0178
Sachiko Yamada
24,25-epoxy-1a-OHD3
C27H42O3 414.621 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect): Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60), osteosarcoma (MG-63) and breast carcinoma (MCF-7) cells : 6, 40 and 18, respectively. Elevation of serum calcium, serum osteocalcin, bone calcium and duodenal calbindin in rachitic chicks : 1, 11, 2 and 2, respectively. Affinity for pig intestinal receptor and human vitamin D binding protein: 16 and 27, respectively. (Ref. 0240)





By epoxidation of the corresponding olefinic precursor which was constructed from Inhoffen-Lythgoe diol. (Ref. 0240)



176
25,26-epoxy-1a-hydroxyvitamin D3 / 25,26-epoxy-1a-hydroxycholecalciferol
(5Z,7E)-(1S,3R)-25,26-epoxy-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0179
Sachiko Yamada
25,26-epoxy-1a-OHD3
C27H42O3 414.621 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60), osteosarcoma (MG-63) and breast carcinoma (MCF-7) cells : 37, 18 and 22, respectively. Elevation of serum calcium, serum osteocalcin, bone calcium and duodenal calbindin in rachitic chicks : 14, 25, 9 and 17, respectively. Affinity for pig intestinal receptor and human vitamin D binding protein : 27 and 76, respectively. (Ref. 0240)





By epoxidation of the corresponding olefinic precursor which was constructed from Inhoffen-Lythgoe diol. (Ref. 0240)



177
24,25-epoxy-1a-hydroxy-23,23-dimethyl-26,27-dinorvitamin D3 / 24,25-epoxy-1a-hydroxy-23,23-dimethyl-26,27-dinorcholecalciferol
(5Z,7E)-(1S,3R)-24,25-epoxy-23,23-dimethyl-26,27-dinor-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0180
Sachiko Yamada
24,25-epoxy-23,23-dimethyl-1a-OH-26,27-dinor-D3
C27H42O3 414.621 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60), osteosarcoma (MG-63) and breast carcinoma (MCF-7) cells : 0, 5 and 0, respectively. Elevation of serum calcium, serum osteocalcin, bone calcium and duodenal calbindin in rachitic chicks : all < 0.1. Affinity for pig intestinal receptor and human vitamin D binding protein : 1 and 0, respectively. (Ref. 0240)





By epoxidation of the corresponding olefinic precursor which was constructed from Inhoffen-Lythgoe diol. (Ref. 0240)



178
25-hydroxy-23-oxovitamin D3 / 25-hydroxy-23-oxocholecalciferol
(5Z,7E)-(3S)-3,25-dihydroxy-9,10-seco-5,7,10(19)-cholestatrien-23-one
VVD0181
Sachiko Yamada
25-OH-23-oxo-D3
C27H42O3 414.621 Download ChemDraw structure file
Affinity for bovine thymus receptor (% of 1,25-(OH)2D3 effect), 2.5 ; Affinity for rat plasma vitamin D binding protein : % of 25-OHD3 effect, 272, % of 1,25-(OH)2D3 effect, 13600. (Ref. 0099>
lmax (nm) 264, lmin (nm) 228 (Ref. 0099)

m/z 414, 356, 323, 136, 118, 58 (Ref. 0099)




Produced as a minor metabolite from 23S,25-(OH)2D3 and a major metabolite from 23R,25-(OH)2D3 when incubated with chick kidney. (Ref. 0099)


179
25-hydroxy-24-oxovitamin D3 / 25-hydroxy-24-oxocholecalciferol
(5Z,7E)-(3S)-3,25-dihydroxy-9,10-seco-5,7,10(19)-cholestatrien-24-one
VVD0182
Sachiko Yamada
25-OH-24-oxo-D3
C27H42O3 414.621 Download ChemDraw structure file
Influences of vitamin D3 metabolites on medullary bone formation; Table (Ref. 0097)
(KBr) spectrum (Ref. 0097)
1H-NMR (d, CDCl3) spectrum (Ref. 0097)
m/z 414 (M+), 271, 253, 136, 118, 59; spectrum (Ref. 0096)


Isolation and identification from Chicken kidney homogenates incubated with 25-OHD3. (Ref. 0096)
Isolation and identification from Rat kidneys perfused with pharmacological concentration of 25-OHD3. (Ref. 0098)
Isolated and identified from blood plasma of chicks given large doses of vitamin D3. (Ref. 0100)
Five step synthesis from 22-phenylsulfonyl-23,24-dinor-5,7-choladien-3b-ol tetrahydropyranyl ether and 1,2-epoxy-3-hydroxy-3-methyl butane. (Ref. 0097)
In vitro, 25-hydroxy-24-oxovitamin D3 is hydroxylated at C(23) to give 23S,25-dihydroxy-24-oxovitamin D3 (Ref. 0102) and then cleaved at 23,24-bond to afford 23-hydroxy-24,25,26,27-tetranorvitamin D3. (Ref. 0105)


180
25-hydroxy-1-oxo-3-epiprevitamin D3 / 25-hydroxy-1-oxo-3-epiprecholecalciferol
(6Z)-(3S)-3,25-dihydroxy-9,10-seco-5(10),6,8-cholestatrien-1-one
VVD0183
Sachiko Yamada
25-OH-1-oxo-3-epipre-D3
C27H42O3 414.621 Download ChemDraw structure file

(95% EtOH) lmax (nm) (emax) 242 (10000), 298 (11200) (Ref. 0182)
1H-NMR (d, CDCl3, 300MHz) 0.71 (3H, 18C-CH3), 0.96 (3H, d, J = sim6.6 Hz, 21C-CH3), 1.21 (6H, s, 26, 27C-2CH3), 1.78 (3H, s, 19C-CH3), 2.4-2.6 (1H, m), 2.70-2.85 (1H, m), 4.16 (1H, m, 3-H), 5.47 (1H, m, 9-H), 6.05 and 6.11 (2H, AB pattern, J = sim11.7 Hz, 6-, 7-H) (Ref. 0182)
(CI, NH3) m/z 415 (M+H, 15), 414 (M+, 7), 396 (M+-H2O, 86), 379 (M+H-2H2O, base), 363 (4), 338 (2), 323 (3), 295 (2), 267 (10), 253 (4), 239 (3), 213 (6), 199 (4), 171 (9), 157 (6), 135 (3), 121 (4), 107 (3), 95 (6), 81 (4), 69 (2) (Ref. 0182)



From 1b,25-dihydroxy-3-epivitamin D3 by Des-Martin oxidation. (Ref. 0182)



181
(6E)-(8S)-8,25-dihydroxy-9,10-seco-4,6,10(19)-cholestatrien-3-one
VVD0184
Sachiko Yamada
8a,25-(OH)2-3-oxo-4,6,10(19)-triene-D3
C27H42O3 414.621 Download ChemDraw structure file

(95 % EtOH) lmax (nm) 295, (log e 4.2) (Ref. 0136)
(KBr) 3210-3600, 2950, 1660, 1565, 1380 cm-1 (Ref. 0136)
1H-NMR (d, CDCl3) spectrum (Ref. 0136)
m/z 414 (M+), 396, 381, 378, 368, 363, 325, 267, 135, 122; spectrum(Ref. 0136)


Isolation and identification in various phagocytic cells [alveolar macrophages, murine myeloid leukemia cells (M1), human promyelocytic leukemia cells (HL-60); human monoblast-like lymphoma cells (U 937) ] (Ref. 0136/0137) and in rat liver microsomes incubated with 25-OHD3.. (Ref. 0138)
Synthesis from 25-OHD3 via regio- and stereoselective 7,8-epoxidation as the key step and the determination of the C(18) stereochemistry of the natural metabolite to be S. (Ref. 0136)



182
(23S)-1a,23-dihydroxy-25,26-didehydrovitamin D3 / (23S)-1a,23-dihydroxy-25,26-didehydrocholecalciferol
(5Z,7E)-(1S,3R,23S)-9,10-seco-5,7,10(19),25-cholestatetraene-1,3,23-triol
VVD0185
Sachiko Yamada
1a,23S-(OH)2-25,26-dehydro-D3
C27H42O3 414.621 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Competitive binding to rat intestinal vitamin D receptor, 0.048. (Ref. 0237)









183
(22E)-(24R)-1a,24-dihydroxy-22,23-didehydrovitamin D3 / (22E)-(24R)-1a,24-dihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R,24R)-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,24-triol
VVD0186
Sachiko Yamada
(22E)-1a,24R-(OH)2-22,23-didehydro-D3
C27H42O3 414.621 Download ChemDraw structure file
Affinity for chick the intestinal receptor : 1/10 as active as 1,25-(OH)2D3. Activities in increasing intestinal calcium transport, serum calcium and inorganic phosphorus concentration and bone ash were determined in compared with 1,25-(OH)2D3 and its 24S-epimer. This compound is less potent than either its 24S-epimer or 1,25-(OH)2D3 in these activities. (Ref. 0241)
(EtOH) lmax (nm) 265, lmin (nm) 228 (Ref. 0241)
1H-NMR (d, CDCl3, 400.5MHz) 0.57 (3H, s, 18-H3), 0.87 (3H, d, J = 6.7 Hz, 26-H3), 0.92 (3H, d, J = 6.7 Hz, 27-H3), 1.04 (3H, d, J = 6.6 Hz, 21-H3), 2.32 (1H, dd, J = 13.7 and 6.6 Hz), 2.60 (1H, dd, J = 13.4 and 3.4 Hz), 2.83 (1H, dd, J = 12.6 and 4.0 Hz), 4.23 (1H, m, 3-H), 4.43 (1H, m, 1-H), 5.00 (1H, br s, W1/2 = 4.3 Hz, 19-H), 5.33 (1H, br s, W1/2 = 4.3 Hz, 19-H), 5.39 (1H, dd, J = 15.2 and 7.1 Hz, 22-H), 5.51 (1H, dd, J = 15.2 and 8.3 Hz, 23-H), 6.01 (1H, d, J = 11.4 Hz, 7-H), 6.38 (1H, d, J = 11.4 Hz, 6-H) (Ref. 0241)
m/z 414 (M+), 396, 378, 363, 360, 345, 335, 317, 287, 269, 251, 249, 152, 135, 134, 109 (Ref. 0241)



Synthesis was started with dinorcholenic acid acetate and achieved via Barton



184
(22E)-(24S)-1a,24-dihydroxy-22,23-didehydrovitamin D3 / (22E)-(24S)-1a,24-dihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R,24S)-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,24-triol
VVD0187
Sachiko Yamada
(22E)-1a,24S-(OH)2-22,23-didehydro-D3
C27H42O3 414.621 Download ChemDraw structure file
Affinity for chick the intestinal receptor : nearly as active as 1,25-(OH)2D3. Activities in increasing intestinal calcium transport, serum calcium and inorganic phosphorus concentration and bone ash were determined in compared with 1,25-(OH)2D3 and its 24R-epimer. This compound is less potent than 1,25-(OH)2D3 in these activities but it more potent than its 24R-epimer. (Ref. 0241)
(EtOH) lmax (nm) 265, lmin (nm) 228 (Ref. 0241)
1H-NMR (d, CDCl3, 400.5MHz) 0.57 (3H, s, 18-H3), 0.87 (3H, d, J = 6.7 Hz, 26-H3), 0.92 (3H, d, J = 6.7 Hz, 27-H3), 1.05 (3H, d, J = 6.6 Hz, 21-H3), 2.32 (1H, dd, J = 13.7 and 6.6 Hz), 2.60 (1H, dd, J = 13.4 and 3.4 Hz), 2.83 (1H, dd, J = 12.6 and 4.0 Hz), 4.23 (1H, m, 3-H), 4.43 (1H, m, 1-H), 5.00 (1H, br s, W1/2 = 4.3 Hz, 19-H), 5.33 (1H, br s, W1/2 = 4.3 Hz, 19-H), 5.37 (1H, dd, J = 15.4 and 7.5 Hz, 22-H), 5.46 (1H, dd, J = 15.4 and 8.3 Hz, 23-H), 6.01 (1H, d, J = 11.4 Hz, 7-H), 6.38 (1H, d, J = 11.4 Hz, 6-H) (Ref. 0241)
m/z 414 (M+), 396, 378, 363, 360, 345, 335, 317, 287, 269, 251, 249, 152, 135, 134, 109 (Ref. 0241)



Synthesis was started with dinorcholenic acid acetate and achieved via Barton



185
1a,25-dihydroxy-9,11-didehydrovitamin D3 / 1a,25-dihydroxy-9,11-didehydrocholecalciferol
(5Z,7E)-(1S,3R)-9,10-seco-5,7,9(11),10(19)-cholestatetraene-1,3,25-triol
VVD0188
Sachiko Yamada
1a,25-(OH)2-9,11-didehydro-D3
C27H42O3 414.621 Download ChemDraw structure file






From de-A,B-cholesta-9(11),25-dien-8-one and A-ring synthon (1-ethynyl-3S,5R-dihydroxy-2-methyl-1-cyclohexene derivative), which was obtained in 6 steps from Carvone, via 9,10-seco-5(10),6,7,9(11),25-cholestapentaene-1,3-diol derivative as the key intermediate. (Ref. 0225)



186
1a,25-dihydroxy-16,17-didehydrovitamin D3 / 1a,25-dihydroxy-16,17-didehydrocholecalciferol
(5Z,7E)-(1S,3R)-9,10-seco-5,7,10(19),16-cholestatetraene-1,3,25-triol
VVD0189
Sachiko Yamada
1a,25-(OH)2-16,17-didehydro-D3
C27H42O3 414.621 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 10 ; Competitive binding to rat intestinal vitamin D receptor, 240 ; Differentiation of human leukemia cells (HL-60), 500. (Ref. 0237)









187
1a,25-dihydroxy-22,23-didehydrovitamin D3 / 1a,25-dihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R)-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,25-triol
VVD0190
Sachiko Yamada
(22E)-1a,25-(OH)2-22,23-didehydro-D3
C27H42O3 414.621 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 10 ; Intestinal calcium absorption in rat, 92 ; Bone calcium mobilization in rat, 133 ; Competitive binding to rat intestinal vitamin D receptor, 122 ; Differentiation of human leukemia cells (HL-60), 125. (Ref. 0237)
[a]d-20 +57.2 deg (c = 0.14 in EtOH) (Ref. 0159)
(MeOH) lmax (nm) (emax) 266 (17300) lmin (nm) 228 (Ref. 0159)
1H-NMR (d, CDCl3, 400MHz) 0.57 (3H, s, 18-CH3), 1.05 (3H, d, J = 6.6 Hz, 21-CH3), 1.20 (6H, s, 26- and 27-CH3), 4.23 (1H, m, 3-H), 4.45 (1H, m, 1-H), 5.02 [1H, m (sharp), 19Z-H], 5.35 [1H, m (sharp), 19E-H], 5.42 (2H, m, 22- and 23-H), 6.04 (1H, d, J = 11.3 Hz, 7-H), 6.39 (1H, d, J = 11.3 Hz, 6-H) (Ref. 0159)
m/z 415 (6.8%) (M++1), 397 (100%) (M++1-H2O), 379 (38%) (M++1-2 times H2O), 287 (6.4%) (M+-side chain), 269 (7.2%), 251 (2.0%), 152 (2.4%), 134 (2.0%) (Ref. 0159)







188
(23E)-1a,25-dihydroxy-23,24-didehydrovitamin D3 / (23E)-1a,25-dihydroxy-23,24-didehydrocholecalciferol
(5Z,7E,23E)-(1S,3R)-9,10-seco-5,7,10(19),23-cholestatetraene-1,3,25-triol
VVD0191
Sachiko Yamada
(23E)-1a,25-(OH)2-23,24-didehydro-D3
C27H42O3 414.621 Download ChemDraw structure file










189
1a,25-dihydroxy-6,7-didehydroprevitamin D3 / 1a,25-dihydroxy-6,7-didehydroprecholecalciferol
(1S,3R)-9,10-seco-5(10),8-cholestadien-6-yne-1,3,25-triol
VVD0192
Sachiko Yamada
1a,25-(OH)2-6,7-dehydro-pre-D3
C27H42O3 414.621 Download ChemDraw structure file










190
1b,25-dihydroxy-6,7-didehydro-3-epiprevitamin D3 / 1b,25-dihydroxy-6,7-didehydro-3-epiprecholecalciferol
(1R,3S)-9,10-seco-5(10),8-cholestadien-6-yne-1,3,25-triol
VVD0193
Sachiko Yamada
1b,25-(OH)2-6,7-didehydro-3-epipre-D3
C27H42O3 414.621 Download ChemDraw structure file










191
(17S,20S)-1a,25-dihydroxy-17,20-methano-21-norvitamin D3 / (17S,20S)-1a,25-dihydroxy-17,20-methano-21-norcholecalciferol
(5Z,7E)-(1S,3R,17S,20S)-17,20-methano-21-nor-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0194
Sachiko Yamada
17S,20S-methano-1a,25-(OH)2-21-nor-D3
C27H42O3 414.621 Download ChemDraw structure file






From 4-hydroxyhydrindanone via introduction of the side chain and A-ring fragment. Stereoselective introduction of 17,20-methano-bridge was achieved by the reaction of 17E(20)-ene CD-fragment with dichlorocarbene followed by reduction with sodium in ethanol. (Ref. 0315)



192
(17S,20R)-1a,25-dihydroxy-17,20-methano-21-norvitamin D3 / (17S,20R)-1a,25-dihydroxy-17,20-methano-21-norcholecalciferol
(5Z,7E)-(1S,3R,17S,20R)-17,20-methano-21-nor-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0195
Sachiko Yamada
17S,20R-methano-1a,25-(OH)2-21-nor-D3
C27H42O3 414.621 Download ChemDraw structure file






From 4-hydroxyhydrindanone via introduction of the side chain and A-ring fragment. Stereoselective introduction of 17,20-methano-bridge was achieved by the reaction of 17Z(20)-ene CD-fragment with dichlorocarbene followed by reduction with sodium in ethanol. (Ref. 0315)



193
(22E)-(24R)-24,25-dihydroxy-22,23-didehydrovitamin D3 / (22E)-(24R)-24,25-dihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(3S,24R)-9,10-seco-5,7,10(19),22-cholestatetraene-3,24,25-triol
VVD0196
Sachiko Yamada
(22E)-24,25-(OH)222,23-didehydro-D3
C27H42O3 414.621 Download ChemDraw structure file

(EtOH) lmax (nm) 265, lmin (nm) 228 (Ref. 0193)
1H-NMR (d, CDCl3) 0.56 (3H, s, 13-Me), 1.05 (3H, d, J = 6 Hz, 20-Me), 1.16 and 1.20 (each 3H, s, 25-Me), 3.83 (1H, d, J = 7 Hz, 24-H), 3.96 (1H, m, 3a-H), 4.83 and 5.06 (each 1H, br s, 19-H2), 5.42 (1H, dd, J = 15.7 Hz, 23-H), 5.60 (1H, dd, J = 15.8 Hz, 22-H), 6.05 and 6.25 (each 1H, d, J = 11 Hz, 6- and 7-H) (Ref. 0193)
m/z 414.3132 (Ref. 0193)







194
(22E)-(24S)-24,25-dihydroxy-22,23-didehydrovitamin D3 / (22E)-(24S)-24,25-dihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(3S,24S)-9,10-seco-5,7,10(19),22-cholestatetraene-3,24,25-triol
VVD0197
Sachiko Yamada
(22E)-24S,25-(OH)2-22,23-didehydro-D3
C27H42O3 414.621 Download ChemDraw structure file

(EtOH) lmax (nm) 265, lmin (nm) 228 (Ref. 0193)
1H-NMR (d, CDCl3) 0.56 (3H, s, 13-Me), 1.04 (3H, d, J = 6 Hz, 20-Me), 1.16 and 1.20 (each 3H, s, 25-Me), 3.86 (1H, d, J = 7 Hz, 24-H), 3.96 (1H, m, 3a-H), 4.84 and 5.07 (each 1H, br s, 19-H2), 5.44 (1H, dd, J = 15.7 Hz, 23-H), 5.64 (1H, dd, J = 15.8 Hz, 22-H), 6.04 and 6.26 (each 1H, d, J = 11 Hz, 6- and 7-H) (Ref. 0193)
m/z 414.3125 (Ref. 0193)







195
calicoferol B
(8S,16S)-3,16-dihydroxy-9,10-seco-1,3,5(10)-cholestatrien-9-one
VVD0198
Sachiko Yamada
calicoferol B
C27H42O3 414.621 Download ChemDraw structure file
Toxic against brine shrimp larvae. (Ref. 0317)




Isolated from a gorgonian of the genus Calicogorgia. (Ref. 0318)




196
(24R,25R)-25,26-epoxy-1a,24-dihydroxyvitamin D3 / (24R,25R)-25,26-epoxy-1a,24-dihydroxycholecalciferol
(5Z,7E)-(1S,3R,24R,25R)-25,26-epoxy-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0199
Sachiko Yamada
25R,26-epoxy-1a,24R-(OH)2D3
C27H42O4 430.620 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for pig intestinal receptor and human vitamin D binding protein : 20 and 73, respectively. Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60), osteosarcoma (MG-63) and breast carcinoma (MCF-7) cells : 12, 160 and 45, respectively. Elevation of serum calcium, serum osteocalcin, bone calcium and duodenal calbindin in rachitic chicks : 1, 3, 1 and < 1, respectively. (Ref. 0240)





By Sharpless kinetic epoxidation of the corresponding olefinic precursor. (Ref. 0243)



197
(24R,25S)-25,26-epoxy-1a,24-dihydroxyvitamin D3 / (24R,25S)-25,26-epoxy-1a,24-dihydroxycholecalciferol
(5Z,7E)-(1S,3R,24R,25S)-25,26-epoxy-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0200
Sachiko Yamada
25S,26-epoxy-1a,24R-(OH)2D3
C27H42O4 430.620 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for pig intestinal receptor and human vitamin D binding protein : 9 and 30, respectively. Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60), osteosarcoma (MG-63) and breast carcinoma (MCF-7) cells : 33, 4 and 34, respectively. Elevation of serum calcium, serum osteocalcin, bone calcium and duodenal calbindin in rachitic chicks : 1, 2, 4 and 1, respectively. (Ref. 0240)





By Sharpless kinetic epoxidation of the corresponding olefinic precursor. (Ref. 0243)



198
(24S,25R)-25,26-epoxy-1a,24-dihydroxyvitamin D3 / (24S,25R)-25,26-epoxy-1a,24-dihydroxycholecalciferol
(5Z,7E)-(1S,3R,24S,25R)-25,26-epoxy-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0201
Sachiko Yamada
25R,26-epoxy-1a,24S-(OH)2D3
C27H42O4 430.620 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for pig intestinal receptor and human vitamin D binding protein : 10 and 7, respectively. Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60), osteosarcoma (MG-63) and breast carcinoma (MCF-7) cells : 44, 7 and 20, respectively. Elevation of serum calcium, serum osteocalcin, bone calcium and duodenal calbindin in rachitic chicks : 3, 2, 1 and 2, respectively. (Ref. 0240)





By Sharpless kinetic epoxidation of the corresponding olefinic precursor. (Ref. 0243)



199
(24S,25S)-25,26-epoxy-1a,24-dihydroxyvitamin D3 / (24S,25S)-25,26-epoxy-1a,24-dihydroxycholecalciferol
(5Z,7E)-(1S,3R,24S,25S)-25,26-epoxy-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0202
Sachiko Yamada
25S,26-epoxy-1a,24S-(OH)2D3
C27H42O4 430.620 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for pig intestinal receptor and human vitamin D binding protein : 5 and 3, respectively. Inhibition of proliferation or differentiation induction of human promyeloid leukemia (HL-60), osteosarcoma (MG-63) and breast carcinoma (MCF-7) cells : 7, 15 and 20, respectively. Elevation of serum calcium, serum osteocalcin, bone calcium and duodenal calbindin in rachitic chicks : 2, < 1, < 1 and < 1, respectively. (Ref. 0240)





By Sharpless kinetic epoxidation of the corresponding olefinic precursor. (Ref. 0243)



200
1a,25-dihydroxy-18-oxovitamin D3 / 1a,25-dihydroxy-18-oxocholecalciferol
(5Z,7E)-(1S,3R)-1,3,25-trihydroxy-9,10-seco-5,7,10(19)-cholestatrien-18-al
VVD0203
Sachiko Yamada
1a,25-(OH)2-18-oxo-D3
C27H42O4 430.620 Download ChemDraw structure file










201
1a,25-dihydroxy-24-oxovitamin D3 / 1a,25-dihydroxy-24-oxocholecalciferol
(5Z,7E)-(1S,3R)-1,3,25-trihydroxy-9,10-seco-5,7,10(19)-cholestatrien-24-one
VVD0204
Sachiko Yamada
1a,25-(OH)2-24-oxo-D3
C27H42O4 430.620 Download ChemDraw structure file
Competition of 1,25-(OH)2D3 and its derivatives for the 3.7 S cytosolic receptors present in intestine and thymus; Table (Ref. 0068)
lmax (nm) 265, lmin (nm) 228 (Ref. 0067)
1H-NMR (d, CDCl3, 200MHz) 6.39 (d, J = 11.2Hz, 6-H), 6.03 (d, J = 11.2 Hz, 7-H), 5.34 (broad s, 19Z-H), 5.01 (broad s, 19E-H), 4.44 (m, 1b-H), 4.24 (m, 3a-H), 1.40 (s, 26C, 27C-CH3), 0.94 (d, J = 5.86 Hz, 21C-CH3), 0.56 (s, 18C-CH3); spectrum (Ref. 0067)
m/z 430 (5, M+), 412 (38, M+-H2O), 394 (59, M+-2H2O), 376 (10, M+-3H2O), 269 (16, M+-side chain), 251 (42, 269-H2O), 152 [24, (A ring+C6+C7)+], 134 (59, 152-H2O); spectrum (Ref. 0067)
m/z 430 (M+), 412, 394, 287, 269, 251, 152, 134; spectrum (Ref. 0102)


Isolation and identification from homogenates of either chick small intestine mucoca or rat kidney incubated with either 1,25-(OH)2D3 or 1,24,25-(OH)3D3. (Ref. 0067)

1,25-(OH)2-24-oxo-D3 is metabolized to 1-OH-tetranor-D3 23-carboxylic acid (calcitroic acid) (Ref. 0070/0073) via 1,23S,25-(OH)3-24-oxo-D3 (Ref. 0067) and 1,23-(OH)2-tetranor-D3 (Ref. 0069) .


202
(23S)-23,25-dihydroxy-24-oxovitamin D3 / (23S)-23,25-dihydroxy-24-oxocholecalciferol
(5Z,7E)-(3S,23S)-3,23,25-trihydroxy-9,10-seco-5,7,10(19)-cholestatrien-24-one
VVD0205
Sachiko Yamada
23S,25-(OH)2-24-oxo-D3
C27H42O4 430.620 Download ChemDraw structure file

lmax (nm) 265, lmin (nm) 228 (Ref. 0103)
(CHCl3) 3500, 2930, 2860, 1708 cm-1 (Ref. 0103)
1H-NMR (d, CDCl3, 100MHz) 0.57 (3H, s, 18-H), 1.09(3H, d, J = 6 Hz, 21-H), 1.42 and 1.44 (each 3H, s, 26- and 27-H), 3.96 (1H, m, 3-H), 4.66 (1H, m, 23-H), 4.84 (1H, bs, 19E-H), 5.07 (1H, bs, 19Z-H), 6.04 (1H, d, J = 11.5 Hz, 7-H), 6.24 (1H, d, J = 11.5 Hz, 6-H) (Ref. 0103)
m/z 430 (M+), 412, 372, 342, 271, 253, 136, 118; spectrum(Ref. 0102)


Isolation and identification from chicken kidney homogenate incubated with 25-OH-24-oxo D3. (Ref. 0102)
Isolation and identification from rat kidneys perfused with pharmacological concentration of 25-OHD3. (Ref. 0098)
Stereoselective synthesis of (23S)-23,25-dihydroxy-24-oxovitamin D3 from 3b-hydroxy-5,7-cholestadien-24-one, and determination of the configulation at C(23) of the natural metabolite. (Ref. 0103)
In vitro, 23S,25-dihydroxy-24-oxovitamin D3 is cleaved at 23,24-bond to afford 23-hydroxy-24,25,26,27-tetranorvitamin D3. (Ref. 0105)
In vivo, 23S,25-(OH)2-24-oxo-D3 is conjugated at 23-hydroxyl group as b-glucuronide to be excreted to bile. (Ref. 0106)


203
(23S,25R)-25-hydroxyvitamin D3 26,23-lactol / (23S,25R)-25-hydroxycholecalciferol 26,23-lactol
(5Z,7E)-(3S,23S,25R)-3,25-dihydroxy-9,10-seco-5,7,10(19)-cholestatrieno-26,23-lactol
VVD0206
Sachiko Yamada
25R-OHD3 26,23S-lactol
C27H42O4 430.620 Download ChemDraw structure file

lmax (nm) 265, lmin (nm) 228 (Ref. 0124)

m/z 430 (M+), 412 (M+-H2O), 342, 309 (342-H2O-CH3), 136, 118; spectrum (Ref. 0124)


Produced by incubating vitamin D supplemented Chick Kidney homogenate with 23S,25R,26-(OH)3D3. (Ref. 0124)
From 25R-OHD3 26,23S-lactone (Ref. 0113) by reduction with diisobutyl alminium hydride. (Ref. 0125)



204
(22E)-(24R)-1a,24,25-trihydroxy-22,23-didehydrovitamin D3 / (22E)-(24R)-1a,24,25-trihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R,24R)-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,24,25-tetrol
VVD0207
Sachiko Yamada
(22E)-1a,24R,25-(OH)3-22,23-didehydro-D3
C27H42O4 430.620 Download ChemDraw structure file
Increase of Intestinal Calcium Transport and Serum Calcium Concentration in Response to Either (22E,24R)-1,24-(OH)2-D22-D3, (22E,24S)-1,24-(OH)2-D22-D3 or 1,25-(OH)2D3. :Table (Ref. 0194)
Increase of Serum Inorganic Phosphorus Concentration and Bone Ash in Response to Either (22E,24R)-1,24-(OH)2-D22-D3, (22E,24S)-1,24-(OH)2-D22-D3 or 1,25-(OH)2D3. : Table (Ref. 0194)
(EtOH) lmax (nm) 265, lmin (nm) 228 (Ref. 0194)
1H-NMR (d, CDCl3, 400.5MHz) 0.57 (3H, s, 18-H3), 0.87 (3H, d, J = 6.7 Hz, 26-H3), 0.92 (3H, d, J = 6.7 Hz, 27-H3), 1.05 (3H, d, J = 6.6 Hz, 21-H3), 2.32 (1H, dd, J = 13.7 and 6.6 Hz), 2.60 (1H, dd, J = 13.4 and 3.4 Hz), 2.83 (1H, dd, J = 12.6 and 4.0 Hz), 4.23 (1H, m, 3-H), 4.43 (1H, m, 1-H), 5.00 (1H, br s, W1/2 = 4.3 Hz, 19-H), 5.33 (1H, br s, W1/2 = 4.3 Hz, 19-H), 5.37 (1H, dd, J = 15.4 and 7.5 Hz, 22-H), 5.46 (1H, dd, J = 15.4 and 8.3 Hz, 23-H), 6.01 (1H, d, J = 11.4 Hz, 7-H), 6.38 (1H, d, J = 11.4 Hz, 6-H) (Ref. 0194)
m/z 414 (M+), 396, 378, 363, 360, 345, 335, 317, 287, 269, 251, 249, 152, 135, 134, 109 (Ref. 0194)







205
(22E)-(24S)-1a,24,25-trihydroxy-22,23-didehydrovitamin D3 / (22E)-(24S)-1a,24,25-trihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R,24S)-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,24,25-tetrol
VVD0208
Sachiko Yamada
(22E)-1a,24S,25-(OH)3-22,23-didehydro-D3
C27H42O4 430.620 Download ChemDraw structure file
Increase of Intestinal Calcium Transport and Serum Calcium Concentration in Response to Either (22E,24R)-1,24-(OH)2-D22-D3, (22E,24S)-1,24-(OH)2-D22-D3 or 1,25-(OH)2D3. : Table(Ref. 0194)
Increase of Serum Inorganic Phosphorus Concentration and Bone Ash in Response to Either (22E,24R)-1,24-(OH)2-D22-D3, (22E,24S)-1,24-(OH)2-D22-D3 or 1,25-(OH)2D3. : Table (Ref. 0194)
(EtOH) lmax (nm) 265, lmin (nm) 228 (Ref. 0194)
1H-NMR (d, CDCl3, 400.5MHz) 0.57 (3H, s, 18-H3), 0.87 (3H, d, J = 6.7 Hz, 26-H3), 0.92 (3H, d, J = 6.7 Hz, 27-H3), 1.04 (3H, d, J = 6.6 Hz, 21-H3), 2.32 (1H, dd, J = 13.7 and 6.6 Hz), 2.60 (1H, dd, J = 13.4 and 3.4 Hz), 2.83 (1H, dd, J = 12.6 and 4.0 Hz), 4.23 (1H, m, 3-H), 4.43 (1H, m, 1-H), 5.00 (1H, br s, W1/2 = 4.3 Hz, 19-H), 5.33 (1H, br s, W1/2 = 4.3 Hz, 19-H), 5.39 (1H, dd, J = 15.2 and 7.1 Hz, 22-H), 5.51 (1H, dd, J = 15.2 and 8.3 Hz, 23-H), 6.01 (1H, d, J = 11.4 Hz, 7-H), 6.38 (1H, d, J = 11.4 Hz, 6-H) (Ref. 0194)
m/z 414 (M+), 396, 378, 363, 360, 345, 335, 317, 287, 269, 251, 249, 152, 135, 134, 109 (Ref. 0194)







206
(22E)-(25R)-1a,25,26-trihydroxy-22,23-didehydrovitamin D3 / (22E)-(25R)-1a,25,26-trihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R,25R)-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,25,26-tetrol
VVD0209
Sachiko Yamada
(22E)-1a,25R,26-(OH)3-22,23-didehydro-D3
C27H42O4 430.620 Download ChemDraw structure file










207
(22E)-(25S)-1a,25,26-trihydroxy-22,23-didehydrovitamin D3 / (22E)-(25S)-1a,25,26-trihydroxy-22,23-didehydrocholecalciferol
(5Z,7E,22E)-(1S,3R,25S)-9,10-seco-5,7,10(19),22-cholestatetraene-1,3,25,26-tetrol
VVD0210
Sachiko Yamada
(22E)-1a,25S,26-(OH)3-22,23-didehydro-D3
C27H42O4 430.620 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Vitamin D receptor binding (chick intestine), 5.5% ; Inhibition of cell (HL-60) proliferation, 50% ; Induction cell (HL-60) differentiation, 100% ; 45Ca retention in kidney in rats, <10%. (Ref. 0297)





By convergent method in which CD ring synthon and A-ring precursor were combined by Wittig-Horner reaction. The desired side chain structure was constructed stereoselectively by 1,3-dipolar cycloaddition of C-23 nitrone with methyl methacrylate as key step. (Ref. 0297)



208
(23S,25R)-1a,25-dihydroxyvitamin D3 26,23-lactol / (23S,25R)-1a,25-dihydroxycholecalciferol 26,23-lactol
(5Z,7E)-(1S,3R,23S,25R)-1,3,25-trihydroxy-9,10-seco- 5,7,10,(19)-cholestatrieno-26,23-lactol
VVD0211
Sachiko Yamada
1a,25R-(OH)2D3 26,23S-lactol
C27H42O5 446.619 Download ChemDraw structure file
Affinity for the chick intestinal receptor : 1/59 as active as 1,25-(OH)2D3. (Ref. 0242)









209
(23R)-1a,23,25-trihydroxy-24-oxovitamin D3 / (23R)-1a,23,25-trihydroxy-24-oxocholecalciferol
(5Z,7E)-(1S,3R,23R)-1,3,23,25-tetrahydroxy-9-10-seco-5,7,10(19)-cholestatrien-24-one
VVD0212
Sachiko Yamada
1a,23R,25-(OH)3-24-oxo-D3
C27H42O5 446.619 Download ChemDraw structure file
The title compound suppressed PTH secretion significantly (p < 0.01) at 10-12 M and is equipotent with 1,25-(OH)2D3, though the affinity of the former for the receptor in paratyroid cells was 10 times less effective than that of the latter. (Ref. 0271)
Mixture (9:1) of 23R and 23S epimers : (neat) 3391.4, 2925.3, 1711.7, 1375.1, 1043.7 cm-1 (Ref. 0271)
13C-NMR (d, CDCl3, 100MHz) major isomer, 217.03, 147.64, 142.87, 133.02, 124.93, 117.19, 111.80, 77.20, 71.01, 70.84, 66.86, 56.90, 56.39, 46.11, 45.27, 42.87, 40.97, 40.50, 33.12, 29.04, 27.77, 27.72, 27.64, 23.53, 22.27, 18.14, 12.08 (Ref. 0271)




Two C(23) epimers of the title compound were synthesized by palladium catalyzed coupling of the appropriate CD ring fragment with A ring enyne as key step. The A-ring precursor was prepared from quinic acid. The configuration at C(23) of natural metabolite produced in neonatal human keratinocytes was determined to be S by direct comparison with the synthetic two epimers on HPLC. (Ref. 0271)



210
(23S)-1a,23,25-trihydroxy-24-oxovitamin D3 / (23S)-1a,23,25-trihydroxy-24-oxocholecalciferol
(5Z,7E)-(1S,3R,23S)-1,3,23,25-tetrahydroxy-9-10-seco-5,7,10(19)-cholestatrien-24-one
VVD0213
Sachiko Yamada
1a,23S,25-(OH)3-24-oxo-D3
C27H42O5 446.619 Download ChemDraw structure file
The title compound suppressed PTH secretion significantly (p < 0.01) at 10-12 M and is equipotent with 1,25-(OH)2D3, though the affinity of the former for the receptor in paratyroid cells was 10 times less effective than that of the latter. (Ref. 0271)
lmax (nm) 265, lmin (nm) 228 (Ref. 0067)
Mixture (9:1) of 23R and 23S epimers : (neat) 3391.4, 2925.3, 1711.7, 1375.1, 1043.7 cm -1 (Ref. 0271)
1H-NMR (d, CDCl3, 200MHz) 6.39 (d, J = 11.2 Hz, 6-H), 6.02 (d, J = 11.2 Hz, 7-H), 5.34 (broad s, 19Z-H), 5.01 (broad s, 19E-H), 4.44 (m, 1b-H), 4.23 (m, 3a-H), 1.10 (d, J = 6.3 Hz, 21C-CH3), 0.57 (s, 18C-CH3); spectrum (Ref. 0067)
13C-NMR (d, CDCl3, 100MHz) major isomer, 217.03, 147.64, 142.87, 133.02, 124.93, 117.19, 111.80, 77.20, 71.01, 70.84, 66.86, 56.90, 56.39, 46.11, 45.27, 42.87, 40.97, 40.50, 33.12, 29.04, 27.77, 27.72, 27.64, 23.53, 22.27, 18.14, 12.08 (Ref. 0271)
m/z 446 (8, M+), 428 (2.7, M+-H2O), 410 (10, M+-2H2O), 388 (6, M+-C3H6O), 370 (17, 388-H2O), 352 (10, 388-2H2O), 287 (2, M+-side chain), 269 (10, 287-H2O), 251 (10, 287-2H2O), 152 [28, (A ring+C6+C7)+], 134 (100, 152-H2O); spectrum(Ref. 0067)


Isolation and identification from homogenates of either chick small intestine mucoca or rat kidney incubated with either 1,25-(OH)2D3 or 1,24,25-(OH)3D3. (Ref. 0067)
Two C(23) epimers of the title compound were synthesized by palladium catalyzed coupling of the appropriate CD ring fragment with A ring enyne as key step. The A-ring precursor was prepared from quinic acid. The configuration at C(23) of natural metabolite produced in neonatal human keratinocytes was determined to be S by direct comparison with the synthetic two epimers on HPLC. (Ref. 0271)
1,23S,25-(OH)3 -24-oxo-D3 is metabolized to 1-OH-tetranor-D3 23-carboxylic acid (calcitroic acid) (Ref. 0070/0073) via 1,23-(OH)2-tetranor-D3. (Ref. 0069)


211
2a-chloro-1b,25-dihydroxyvitamin D3 / 2a-chloro-1b,25-dihydroxycholecalciferol
(5Z,7E)-(1S,2S,3R)-2-chloro-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0214
Sachiko Yamada
2a-chloro-1b,25-(OH)2D3
C27H43ClO3 451.081 Download ChemDraw structure file
Affinity for rat intestinal VDR, 10 % of the activity of 25-OHD3 ; gene transcription (VDRE-CAT assay), nearly 10,000 times weaker than 1,25-(OH)2D3. (Ref. 0325)
CH3OH :173-179 degC (Ref. 0325)
(CH3OH) lmax (nm) (emax) 264 (15300) (Ref. 0325)
1H-NMR (d, CDCl3, 400MHz) 0.50 (3H, s, 18-H), 0.91 (3H, d, J = 6.3 Hz, 21-H), 1.19 (6H, s, 26- and 27-H), 2.25 (1H, m, 4b-H), 2.54 (1H, t, J = 9.7 Hz, 4a-H), 2.71 (1H, m, 9b-H), 3.81-3.83 (2H, m, 2b-H and 3a-H), 4.12 (1H, m, 1a-H), 5.11 and 5.56 (2H, 2timest, J = 2 Hz, 19-H), 5.94 and 6.38 (2H, 2timesd, J = 11.3 Hz, 7- and 6-H) (Ref. 0325)




From 1b,2b-epoxy-25-hydroxy-7-dehydrocholesterol via the reaction with hydrogen chloride followed by photochemical transformation. (Ref. 0325)



212
6-fluorovitamin D3 / 6-fluorocholecalciferol
(5E,7E)-(3S)-6-fluoro-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0215
Sachiko Yamada
6-F-D3
C27H43FO 402.628 Download ChemDraw structure file
Ability to compete with tritiated 1,25-(OH)2-D3 for binding to the chick intestinal receptor (RCI) : 0.26% of 1,25-(OH)2D3 effect. The title compound showed no biological action on either intestinal calcium absorption (ICA) or bone calcium mobilization at doses up to 130 nmol but it significantly inhibited vitamin D-mediated ICA. (Ref. 0294)
(Hexane) lmax (nm) (emax) 268 (10300) (Ref. 0295)
1H-NMR (d, CDCl3) 6.00 (1H, br d, J = 6.0 Hz), 5.10 (1H, s), 4.93 (1H, s), 4.02 (1H, m), 0.95 (3H, d, J = 6.4 Hz), 0.87 (6H, d, J = 6.4 Hz), 0.66 (3H, s) (Ref. 0295)
m/z (relative intensity) 402 (parent, 50), 369 (67), 315 (26), 314 (100), 299 (21), 281 (23), 271 (25), 299 (33), 163 (30), 161 (32), 147 (23), 145 (30), 133 (30), 109 (29), 107 (32), 105 (30), 95 (40), 81 (41) (Ref. 0295)



From 6-fluorocholesteryl acetate via conventional photochemical conversion of the corresponding 7-dehydro derivative. (Ref. 0295)



213
(10Z)-19-fluorovitamin D3 / (10Z)-19-fluorocholecalciferol
(5Z,7E,10Z)-(3S)-19-fluoro-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0216
Sachiko Yamada
(10Z)-19-F-D3
C27H43FO 402.628 Download ChemDraw structure file

(95% EtOH) lmax (nm) 263 (Ref. 0333)
1H-NMR (d, CDCl3) 0.55 (3H, s, 18-H), 0.86 and 0.87 (each 3H, d, J = 6.6 Hz, 26- and 27-H), 0.92 (3H, d, J = 6.2 Hz, 21-H), 2.60 (1H, dd, J = 13.2 and 3.5 Hz, 4-H), 2.81 (1H, m, 9-H), 3.95 (1H, tt, J = 7.3 and 3.6 Hz, 3-H), 5.63 (1H, d, J = 11.3 and 5.3 Hz, 7-H), 6.37 (1H, d, J = 11.3 Hz, 6-H), 6.47 (1H, d, J = 85.5 Hz, 19-H) (Ref. 0333)
19F-NMR (d, CDCl3) -127.5 (d, J = 85.5 Hz) (Ref. 0333)




From vitamin D3 via elimination of the exocyclic methylene and introduction of a fluoromethylene group as key steps. (Ref. 0333)



214
(10E)-19-fluorovitamin D3 / (10E)-19-fluorocholecalciferol
(5Z,7E,10E)-(3S)-19-fluoro-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0217
Sachiko Yamada
(10E)-19-F-D3
C27H43FO 402.628 Download ChemDraw structure file

(EtOH) lmax (nm) (emax) 260 (20900) (Ref. 0333)
1H-NMR (d, CDCl3) 0.53 (3H, s, 18-H), 0.86 and 0.87 (each 3H, d, J = 6.6 Hz, 26- and 27-H), 0.92 (3H, d, J = 6.4 Hz, 21-H), 2.56 (2H, m), 2.78 (1H, m), 3.93 (1H, m, 3-H), 5.93 and 6.28 (each 1H, d, J = 11.1 Hz, 6, 7-H), 6.51 (1H, d, J = 87.4 Hz, 19-H) (Ref. 0333)
19F-NMR (d, CDCl3) -132.5 (d, J = 87.4 Hz, 19-F) (Ref. 0333)
m/z 402 (M+, 36), 384 (21), 382 (8), 364 (16), 317 (5), 289 (13), 271 (19), 269 (6), 259 (11), 154 (45), 136 (70), 135 (100) (Ref. 0333)



From vitamin D3 by regioselective electrophilic 19-fluorination of its sulfur dioxide adduct as a key step. (Ref. 0346)



215
(5E,10Z)-19-fluorovitamin D3 / (5E,10Z)-19-fluorocholecalciferol
(5E,7E,10Z)-(3S)-19-fluoro-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0218
Sachiko Yamada
(5E,10Z)-19-F-D3
C27H43FO 402.628 Download ChemDraw structure file

(EtOH) lmax (nm) 270 (Ref. 0333)
1H-NMR (d, CDCl3) 0.56 (3H, s, 18-H), 0.867 and 0.871 (each 3H, d, J = 6.6 Hz, 26- and 27-H), 0.92 (3H, d, J = 6.4 Hz, 21-H), 2.83 (2H, m), 3.86 (1H, m, 3-H), 5.93 and 6.63 (each 1H, d, J = 11.5 Hz, 6, 7-H), 6.51 (1H, d, J = 86.6 Hz, 19-H) (Ref. 0333)
19F-NMR (d, CDCl3) -134.8 (d, J = 86.6 Hz, 19-F) (Ref. 0333)
m/z 402 (M+, 100), 384 (7), 382 (4), 364 (4), 317 (20), 289 (42), 271 (18), 269 (7), 259 (47), 194 (12), 176 (16), 154 (20), 136 (39), 135 (67) (Ref. 0333)



From vitamin D3 by regioselective electrophilic 19-fluorination of its sulfur dioxide adduct as a key step. (Ref. 0346)



216
(5E,10E)-19-fluorovitamin D3 / (5E,10E)-19-fluorocholecalciferol
(5E,7E,10E)-(3S)-19-fluoro-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0219
Sachiko Yamada
(5E,10E)-19-F-D3
C27H43FO 402.628 Download ChemDraw structure file

(EtOH) lmax (nm) 209, 269 (Ref. 0333)
1H-NMR (d, CDCl3) 0.55 (3H, s, 18-H), 0.868 and 0.873 (each 3H, d, J = 6.6 Hz, 26- and 27-H), 0.92 (3H, d, J = 6.7 Hz, 21-H), 2.67 (1H, m), 2.82 (2H, m), 3.88 (1H, m, 3-H), 5.83 and 6.35 (each 1H, d, J = 11.5 Hz, 6, 7-H), 6.69 (1H, d, J = 86.7 Hz, 19-H) (Ref. 0333)
19F-NMR (d, CDCl3) -135.4 (d, J = 86.7 Hz, 19-F) (Ref. 0333)
m/z 402 (M+, 84), 384 (7), 382 (3), 364 (4), 317 (11), 289 (25), 271 (13), 269 (7), 259 (21), 194 (6), 176 (13), 154 (50), 136 (89), 135 (100) (Ref. 0333)



From vitamin D3 by regioselective electrophilic 19-fluorination of its sulfur dioxide adduct as a key step. (Ref. 0346)



217
22-fluorovitamin D3 / 22-fluorocholecalciferol
(5Z,7E)-(3S)-22-fluoro-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0220
Sachiko Yamada
22-F-D3
C27H43FO 402.628 Download ChemDraw structure file
Serosal/Mucosal Ratio after Administration of Sterols or Vehicle. Mean pm SEM (n=Number of Animals). : (Ref. 0162)
Serum Calcium (mg/dL) after Administration of Sterols or Vehicle. Mean pm SEM (n=Number). (Ref. 0162)
Serosal/Mucosal Ratio and Serum Calcium Response Following Administration of Vitamin D3 or 22-Fluorovitamin D3. Mean pm SEM (n=Number). (Ref. 0162)
Calcium Binding Protein Induction by 22-Fluorovitamin D3 in Duodenal Organ Culture. (Ref. 0162)
(EtOH) lmax (nm) 264, lmin (nm) 227 (Ref. 0162)
1H-NMR (d, CDCl3) 3.82 (1H, m, 3a-H), 4.44 (1H, dm, J = 48.2 Hz, 22-H), 4.82 (1H, d, J = 2.24 Hz, 19-H), 5.05 (1H, d, J = 2.24 Hz, 19-H), 6.01 and 6.25 (2H, ABq, J = 11.22 Hz, 6- and 7-H) (Ref. 0162)
m/z 402 (M+, 80.51), 384 (M+-H2O, 8.05), 382 (M+-HF, 8.88), 369 (25.11), 136 (25.51), 118 (53.82) (Ref. 0162)







218
(5Z,10Z)-19-fluoro-1a-hydroxyvitamin-D3 / (5Z,10Z)-19-fluoro-1a-hydroxycholecalciferol
(5Z,7E,10Z)-(1S,3R)-19-fluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0221
Sachiko Yamada
(5Z,10Z)-19-F-1a-OHD3
C27H43FO2 418.628 Download ChemDraw structure file

(EtOH) lmax (nm) 262 (Ref. 0333)
1H-NMR (d, CDCl3) 0.53 (3H, s, 18-H), 0.863 and 0.867 (each 3H, d, J = 6.6 Hz, 26- and 27-H), 0.91 (3H, d, J = 6.3 Hz, 21-H), 2.19 (1H, m), 2.32 (1H, m), 2.68 (1H, m), 2.80 (1H, m, 9-H), 4.16 (1H, m, 3-H), 5.09 (1H, br s, 1-H), 5.90 (1H, d, J = 11.1 Hz, 7-H), 6.46 (1H, d, J = 11.1 Hz, 6-H), 6.50 (1H, d, J = 86.0 Hz, 19-H) (Ref. 0333)
19F-NMR (d, CDCl3) -129.8 (d, J = 86.0 Hz) (Ref. 0333)
m/z 418 (M+, 6), 400 (5), 398 (5), 380 (10), 362 (52), 347 (8), 305 (5), 287 (5), 285 (5), 267 (8), 249 (34), 195 (35), 135 (100) (Ref. 0333)







219
(5Z,10E)-19-fluoro-1a-hydroxyvitamin-D3 / (5Z,10E)-19-fluoro-1a-hydroxycholecalciferol
(5Z,7E,10E)-(1S,3R)-19-fluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0222
Sachiko Yamada
(5Z,10E)-19-F-1a-OHD3
C27H43FO2 418.628 Download ChemDraw structure file

(EtOH) lmax (nm) 264 (Ref. 0333)
1H-NMR (d, CDCl3) 0.54 (3H, s, 18-H), 0.86 and 0.87 (each 3H, d, J = 6.6 Hz, 26- and 27-H), 0.92 (3H, d, J = 6.3 Hz, 21-H), 2.14 (1H, m), 2.28 (1H, dd, J = 13.0, 8.6 Hz, 4-H), 2.66 (1H, dd, J = 13.0, 3.9 Hz, 4-H), 2.82 (1H, m, 9-H), 4.20 (1H, m, 3-H), 4.44 (1H, dd, J = 9.2, 4.7 Hz, 1-H), 5.62 (1H, dd, J = 11.3, 5.4 Hz, 7-H), 6.52 (1H, d, J = 11.3 Hz, 6-H), 6.70 (1H, d, J = 84.0 Hz, 19-H) (Ref. 0333)
19F-NMR (d, CDCl3) -127.8 (broard s) (Ref. 0333)
m/z 418 (M+, 55), 400 (7), 398 (12), 380 (22), 362 (100), 347 (21), 305 (16), 287 (9), 285 (10), 267 (16), 249 (68), 195 (52), 135 (43) (Ref. 0333)







220
(5E,10Z)-19-fluoro-1a-hydroxyvitamin-D3 / (5E,10Z)-19-fluoro-1a-hydroxycholecalciferol
(5E,7E,10Z)-(1S,3R)-19-fluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0223
Sachiko Yamada
(5E,10Z)-19-F-1a-OHD3
C27H43FO2 418.628 Download ChemDraw structure file

(EtOH) lmax (nm) 269 (Ref. 0333)
1H-NMR (d, CDCl3) 0.55 (3H, s, 18-H), 0.868 and 0.872 (each 3H, d, J = 6.5 Hz, 26- and 27-H), 0.93 (3H, d, J = 6.2 Hz, 21-H), 2.31 (1H, m), 2.81 (1H, m, 9-H), 3.15 (1H, m, 4-H), 4.15 (1H, m, 3-H), 5.05 (1H, d, J = 3.2 Hz, 1-H), 5.87 (1H, d, J = 11.4 Hz, 7-H), 6.38 (1H, d, J = 11.4 Hz, 6-H), 6.69 (1H, d, J = 85.6 Hz, 19-H) (Ref. 0333)
19F-NMR (d, CDCl3) -133.2 (d, J = 85.6 Hz) (Ref. 0333)
m/z 418 (M+, 12), 398 (26), 380 (31), 362 (51), 347 (13), 305 (7), 287 (7), 285 (15), 267 (26), 249 (44), 195 (41), 135 (100) (Ref. 0333)







221
(5E,10E)-19-fluoro-1a-hydroxyvitamin-D3 / (5E,10E)-19-fluoro-1a-hydroxycholecalciferol
(5E,7E,10E)-(1S,3R)-19-fluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0224
Sachiko Yamada
(5E,10E)-19-F-1a-OHD3
C27H43FO2 418.628 Download ChemDraw structure file

(EtOH) lmax (nm) 272 (Ref. 0333)
1H-NMR (d, CDCl3) 0.57 (3H, s, 18-H), 0.87 and 0.88 (each 3H, d, J = 6.6 Hz, 26- and 27-H), 0.93 (3H, d, J = 6.3 Hz, 21-H), 2.19 (1H, m), 2.32 (1H, m), 2.68 (1H, m), 2.80 (1H, m, 9-H), 3.07 (1H, dd, 4-H), 4.19 (1H, m, 3-H), 4.34 (1H, br s, 1-H), 5.97 (1H, d, J = 11.6 Hz, 7-H), 6.68 (1H, d, J = 11.6 Hz, 6-H), 6.74 (1H, d, J = 83.4 Hz, 19-H) (Ref. 0333)
19F-NMR (d, CDCl3) -132.8 (d, J = 83.4 Hz) (Ref. 0333)
m/z 418 (M+, 100), 398 (61), 380 (23), 362 (54), 347 (14), 305 (30), 287 (19), 285 (36), 267 (30), 249 (53), 195 (40), 135 (88) (Ref. 0333)







222
25-fluoro-1a-hydroxyvitamin D3 / 25-fluoro-1a-hydroxycholecalciferol
(5Z,7E)-(1S,3R)-25-fluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0225
Sachiko Yamada
1a-OH-25-F-D3
C27H43FO2 418.628 Download ChemDraw structure file
Binding affinity for chick intestinal cytosol protein : 25-F-1-OHD3 is 315 times less efective than 1,25-(OH)2D3 in competitive protein-binding assay. Intestinal calcium transport and bone mineral mobilization : 25-F-1-OHD3 is about 50 times less active than 1,25-(OH)2D3. Antirachitic potency : 25-F-1-OHD3 is 40 times less potent than 1,25-(OH)2D3. (Ref. 0229)

m/z 418 (M+), 380, 152, 134 (Ref. 0229)







223
(24R)-25-fluoro-24-hydroxyvitamin D3 / (24R)-25-fluoro-24-hydroxycholecalciferol
(5Z,7E)-(3S,24R)-25-fluoro-9,10-seco-5,7,10(19)-cholestatriene-3,24-diol
VVD0226
Sachiko Yamada
24R-OH-25-F-D3
C27H43FO2 418.628 Download ChemDraw structure file










224
1a-fluoro-25-hydrovitamin D3 / 1a-fluoro-25-hydrocholecalciferol
(5Z,7E)-(1S,3R)-3-fluoro-9,10-seco-5,7,10(19)-cholestatriene-3,25-diol
VVD0227
Sachiko Yamada
1a-F-25-OHD3
C27H43FO2 418.628 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100. (Ref. 0237)









225
24-fluoro-25-hydroxyvitamin D3 / 24-fluoro-25-hydroxycholecalciferol
(5Z,7E)-(3S)-24-fluoro-9,10-seco-5,7,10(19)-cholestatriene-3,25-diol
VVD0228
Sachiko Yamada
24-F-25-OHD3
C27H43FO2 418.628 Download ChemDraw structure file

(EtOH) lmax (nm) 263, lmin (nm) 228 (Ref. 0199)

m/z 418 (M+), 403, 400, 385, 359, 271, 253, 136, 118 (Ref. 0199)







226
(24R)-25-fluoro-1a,24-dihydroxyvitamin D3 / (24R)-25-fluoro-1a,24-dihydroxycholecalciferol
(5Z,7E)-(1S,3R,24R)-25-fluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,24-triol
VVD0229
Sachiko Yamada
25-F-1a,24R-(OH)2-D3
C27H43FO3 434.627 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Competitive binding to rat intestinal vitamin D receptor, 0.165. (Ref. 0237)








227
(10Z)-19-fluoro-1a,25-dihydroxyvitamin D3 / (10Z)-19-fluoro-1a,25-dihydroxycholecalciferol
(5Z,7E,10Z)-(1S,3R)-19-fluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0230
Sachiko Yamada
(10Z)-19-F-1a,25-(OH)2D3
C27H43FO3 434.627 Download ChemDraw structure file

(95% EtOH) lmax (nm) 261 (Ref. 0333)
1H-NMR (d, CDCl3) 0.53 (3H, s, 18-H), 0.93 (3H, d, J = 6.4 Hz, 21-H), 1.21 (6H, s, 26- and 27-H), 2.18 (1H, t, J = 11.6 Hz, 4-H), 2.31 (1H, m, 2-H), 2.67 (1H, dm, J = 11.6 Hz, 4-H), 2.80 (1H, m, 9-H), 4.17 (1H, tt, J = 10.9 and 4.4 Hz, 3-H), 5.08 (1H, t, J = 3.1 Hz, 1-H), 5.90 (1H, d, J = 11.1 Hz, 7-H), 6.46 (1H, d, J = 11.1 Hz, 6-H), 6.50 (1H, d, J = 86.1 Hz, 19-H) (Ref. 0333)
19F-NMR (d, CDCl3) -129.6 (d, J = 86.1 Hz) (Ref. 0333)
13C-NMR (d, CDCl3) 12.3, 19.0, 21.0, 22.5, 23.6, 27.9, 29.4, 29.6, 29.9, 36.3, 36.6, 40.7, 42.0, 44.6, 46.2, 46.3, 56.5, 56.7, 63.1 (d, J = 6.2 Hz), 66.5, 71.4, 116.6, 121.4 (d, J = 4.1 Hz), 126.1, 126.7 (d, J = 6.1 Hz), 144.5, 146.5 (d, J = 267.9 Hz) (Ref. 0333)
m/z 434 (M+, 13), 416 (17), 398 (13), 396 (18), 378 (25), 360 (52), 305 (8), 287 (16), 285 (11), 269 (9), 267 (13), 249 (32), 135 (100) (Ref. 0333)



From (1) vitamin D2, via side chain cleavage, side chain introduction, 1a-hydroxylation, and 19-fluorination of 6,19-sulfur-dioxide adduct of the resulting 1a,25-dihydroxyvitamin D3 derivative as key steps or (2) from (5E)-1a,25-dihydroxyvitamin D3 via elimination of the exocyclic methylene and introduction of a fluoromethylene group as key steps. (Ref. 0345)



228
(10E)-19-fluoro-1a,25-dihydroxyvitamin D3 / (10E)-19-fluoro-1a,25-dihydroxycholecalciferol
(5Z,7E,10E)-(1S,3R)-19-fluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0231
Sachiko Yamada
(10E)-19-F-1a,25-(OH)2D3
C27H43FO3 434.627 Download ChemDraw structure file

(95% EtOH) lmax (nm) 264 (Ref. 0333)
1H-NMR (d, CDCl3) 0.54 (3H, s, 18-H), 0.93 (3H, d, J = 6.4 Hz, 21-H), 1.21 (6H, s, 26- and 27-H), 2.13 (1H, m, 2-H), 2.27 (1H, dd, J = 13.0 and 8.5 Hz, 4-H), 2.66 (1H, dd, J = 13.0 and 3.8 Hz, 4-H), 2.82 (1H, m, 9-H), 4.20 (1H, tt, J = 8.5 and 3.8 Hz, 3-H), 4.43 (1H, dd, J = 5.5 and 3.8 Hz, 1-H), 5.63 (1H, d, J = 11.3 and 5.4 Hz, 7-H), 6.51 (1H, d, J = 11.3 Hz, 6-H), 6.70 (1H, d, J = 83.8 Hz, 19-H) (Ref. 0333)
19F-NMR (d, CDCl3) -128.0 (br. signal) (Ref. 0333)
13C-NMR (d, CDCl3) 12.2, 19.0, 21.0, 22.4, 23.8, 27.6, 29.36, 29.39, 29.5, 36.3, 36.6, 40.7, 43.2, 44.6, 45.1, 46.1, 56.5, 56.8, 66.8, 67.7 (d, J = 9.5 Hz), 71.4, 117.9 (d, J = 3.0 Hz), 122.0 (d, J = 4.8 Hz), 124.9, 126.7, 143.4 (d, J = 265.2 Hz), 144.4 (Ref. 0333)
m/z 434 (M+, 28), 416 (31), 398 (13), 396 (11), 378 (20), 360 (100), 305 (16), 287 (14), 285 (10), 269 (14), 267 (15), 249 (69), 135 (42) (Ref. 0333)



From (5E)-1a,25-dihydroxyvitamin D3 via elimination of the exocyclic methylene and introduction of a fluoromethylene group as key steps. (Ref. 0345)



229
(5E,10Z)-19-fluoro-1a,25-dihydroxyvitamin D3 / (5E,10Z)-19-fluoro-1a,25-dihydroxycholecalciferol
(5E,7E,10Z)-(1S,3R)-19-fluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0232
Sachiko Yamada
(5E,10Z)-19-F-1a,25-(OH)2D3
C27H43FO3 434.627 Download ChemDraw structure file

(95% EtOH) lmax (nm) 269 (Ref. 0333)
1H-NMR (d, CDCl3) 0.56 (3H, s, 18-H), 0.95 (3H, d, J = 6.4 Hz, 21-H), 1.22 (6H, s, 26- and 27-H), 2.31 (1H, m), 2.81 (1H, m, 9-H), 3.15 (1H, dm, J = 13.2 Hz, 4-H), 4.16 (1H, tt, J = 11.0 and 4.3 Hz, 3-H), 5.05 (1H, br s, 1-H), 5.87 (1H, d, J = 11.5 Hz, 7-H), 6.38 (1H, d, J = 11.5 Hz, 6-H), 6.69 (1H, d, J = 86.5 Hz, 19-H) (Ref. 0333)
19F-NMR (d, CDCl3) -133.2 (d, J = 86.5 Hz) (Ref. 0333)
13C-NMR (d, CD2Cl2-CD3OD = 2 : 1) 12.3, 19.1, 21.5, 22.8, 24.1, 28.2, 29.0, 29.1, 29.6, 36.8, 37.1, 37.9, 41.1, 42.0, 44.8, 46.5, 57.1, 57.3, 62.5 (d, J = 5.9 Hz), 65.4, 71.3, 116.3, 122.8, 127.6 (d, J = 6.2 Hz), 128.4 (d, J = 6.2 Hz), 144.1 (d, J = 266.1 Hz), 145.6 (Ref. 0333)
m/z 434 (M+, 25), 416 (18), 398 (10), 396 (19), 378 (15), 360 (61), 305 (13), 287 (18), 285 (21), 269 (15), 267 (21), 249 (53), 135 (100) (Ref. 0333)



From (1) vitamin D2, via side chain cleavage, side chain introduction, 1a-hydroxylation, and 19-fluorination of 6,19-sulfur-dioxide adduct of the resulting 1a,25-dihydroxyvitamin D3 derivative as key steps or (2) from (5E)-1a,25-dihydroxyvitamin D3 via elimination of the exocyclic methylene and introduction of a fluoromethylene group as key steps. (Ref. 0345)



230
(5E,10E)-19-fluoro-1a,25-dihydroxyvitamin D3 / (5E,10E)-19-fluoro-1a,25-dihydroxycholecalciferol
(5E,7E,10E)-(1S,3R)-19-fluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0233
Sachiko Yamada
(5E,10E)-19-F-1a,25-(OH)2D3
C27H43FO3 434.627 Download ChemDraw structure file

(95% EtOH) lmax (nm) 269 (Ref. 0333)
1H-NMR (d, CDCl3) 0.58 (3H, s, 18-H), 0.95 (3H, d, J = 6.4 Hz, 21-H), 1.22 (6H, s, 26- and 27-H), 2.25 (1H, m), 2.68 (1H, m), 2.81 (1H, m, 9-H), 3.07 (1H, dd, J = 13.7 and 3.7 Hz, 4-H), 4.19 (1H, tt, J = 10.0 and 4.4 Hz, 3-H), 4.34 (1H, t, J = 3.6 Hz, 1-H), 5.97 (1H, d, J = 11.5 Hz, 7-H), 6.68 (1H, d, J = 11.5 Hz, 6-H), 6.75 (1H, d, J = 83.4 Hz, 19-H) (Ref. 0333)
19F-NMR (d, CDCl3) -132.6 (d, J = 83.4 Hz) (Ref. 0333)
13C-NMR (d, CD2Cl2-CD3OD = 2 : 1) 12.3, 19.1, 21.5, 22.9, 24.2, 28.2, 29.0, 29.1, 29.6, 36.8, 37.1, 37.2, 41.2, 42.5, 44.9, 46.5, 57.2, 57.3, 65.6, 67.7 (d, J = 9.0 Hz), 71.3, 116.5, 125.7 (d, J = 6.1 Hz), 127.7 (d, J = 5.7 Hz), 145.6, 145.8 (d, J = 264.4 Hz) (Ref. 0333)
m/z 434 (M+, 59), 416 (35), 398 (19), 396 (33), 378 (21), 360 (52), 305 (31), 287 (32), 285 (31), 269 (30), 267 (36), 249 (66), 135 (100) (Ref. 0333)



From (5E)-1a,25-dihydroxyvitamin D3 via elimination of the exocyclic methylene and introduction of a fluoromethylene group as key steps. (Ref. 0345)



231
24R-fluoro-1a,25-dihydroxyvitamin D3 / 24R-fluoro-1a,25-dihydroxycholecalciferol
(5Z,7E)-(1S,3R,24R)-24-fluoro-9,10-seco-5,7,10(19)-cholestatriene-1,3,25-triol
VVD0234
Sachiko Yamada
24R-F-1a,25-(OH)2D3
C27H43FO3 434.627 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Inhibition of proliferation of human keratinocytes in culture, 100 ; Intestinal calcium absorption in rat, 65 ; Bone calcium mobilization in rat, 40 ; Competitive binding to rat intestinal vitamin D receptor, 115 ; Differentiation of human leukemia cells (HL-60), 30. (Ref. 0237)
[a]d-25 +67.9 deg (c = 0.52 in MeOH) (Ref. 0191)
(EtOH) lmax (nm) (emax) 213 (12500), 265 (16385) (Ref. 0191)
(CHCl3) 3420 (OH), 1635 (C=C) cm-1 (Ref. 0191)
1H-NMR (d, CDCl3, 200MHz) 0.56 (3H, s, CH3), 0.95 (3H, d, J = 7 Hz, CHCH3), 1.22 and 1.24 (6H, 2 s, CMe2), 2.33 (1H, m), 2.64 (1H, m), 2.84 (1H, m), 4.21 (1H, d m, J = 48 Hz, CHF), 4.26 (1H, br s, CHO), 4.46 (1H, br s, CHO), 5.01 (1H, s, vinyl CH), 5.33 (1H, s, vinyl CH), 6.03 (1H, d, J = 12 Hz, vinyl CH), 6.39 (1H, d, J = 12 Hz, vinyl CH) (Ref. 0191)
m/z 434 (M+, 13), 416 (11), 398 (3), 375 (2), 287 (7), 152 (36), 134 (100) (Ref. 0191)







232
1a,25-dihydroxy-24-oxo-23-azavitamin D2 / 1a,25-dihydroxy-24-oxo-23-azaergocalciferol
(5Z,7E)-(1S,3R,24R)-23-aza-22-oxo-9,10-seco-5,7,10(19)-ergostatriene-1,3,25-triol
VVD0235
Sachiko Yamada
C27H43NO4 445.635 Download ChemDraw structure file
The analogue showed almost no affinity to the chick cytosol vitamin D receptor. (Ref. 0259)
[a]D +1.5 deg (c = 0.0023 in EtOH) (Ref. 0259)
(EtOH) lmax (nm) (emax) 265 (18300) (Ref. 0259)
(CHCl3) 3441, 1651 cm-1 (Ref. 0259)
1H-NMR (d, CDCl3, 400MHz) 0.56 (3H, s), 1.14 (3H, d, J = 7.0 Hz), 1.20 (3H, s), 1.21 (3H, d, J = 6.3 Hz), 1.23 (3H, s), 3.89 (1H, dq, J = 8.2, 6.3 Hz), 4.23 (1H, m), 4.43 (1H, m), 4.99 (1H, s), 5.32 (1H, t, J = 1.8 Hz), 6.02 (1H, d, J = 11.3 Hz), 6.38 (1H, d, J = 11.5 Hz) (Ref. 0259)
m/z 445 (M+), 427 (M+-H2O), 409 (M+-2H2O) (Ref. 0259)

HPLC : Lichrosorb Si-60, 10 times 250 mm ; mobile phase, isoPrOH-CH2Cl2 (13 : 87). Zorbax-SIL,4.6 times 250 mm times 2 ; mobile phase, hexane-CH2Cl2-MeOH-isoPrOH (60 : 30 : 5 : 5). (Ref. 0259)

Condensation of the steroidal 20-carboxylic acid with the requisite side-chain amine, followed by the usual ring opening reactions, gave the amide analogue. (Ref. 0259)



233
1a-hydroxy-3-deoxyvitamin D3 / 1a-hydroxy-3-deoxycholecalciferol
(5Z,7E)-(1S)-9,10-seco-5,7,10(19)-cholestatrien-1-ol
VVD0236
Sachiko Yamada
3-deoxy-1a-OHD3
C27H44O 384.638 Download ChemDraw structure file
Intestinal Calcium Transport and Bone Calcium Mobilization Activity of Analog 4* (3-deoxy-1a-hydroxyvitamin D3) and 3* (1a-OH-D3). (Ref. 0179)
lmax (nm) 264.5, lmin (nm) 229 (Ref. 0179)

m/z 384 (M+), 366, 271, 253, 136 (Ref. 0179)



From 1a,2a-epoxy-6-ethylenedioxycholestan-3-one: treatment with hydrazine hydrate, catalytic reduction, introduction of 5,7-diene function by conventional method and photochemical followed by thermal isomerization. (Ref. 0179)
From 1a-acetoxycholesterol tosylate: reduction of the tosylate function, introduction of 5,7-diene function and photochemical followed by thermal isomerization. (Ref. 0179)



234
vitamin D3 / cholecalciferol / calciol
(5Z,7E)-(3S)-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0237
Sachiko Yamada
D3
C27H44O 384.638 Download ChemDraw structure file
Activities of vitamin D3 in intestinal calcium transport and bone calcium mobilization were compared with those of 25-OHD3: Tables (Ref. 0014)
84-85 degC (Ref. 0001)
[a]d-25 +51.9 deg (c = 1.6 in CHCl3) (Ref. 0001)
(95% EtOH or Hexane) lmax (nm) (e) 264.5 (18200) (Ref. 0001)
1H-NMR (d, CDCl3, 300MHz) 0.54 (3 H, s, 18-CH3), 0.87 (6 H, d, J = 6.5 Hz, 26-, 27-CH3), 0.92 (3 H, d, J = 6 Hz, 21-CH3), 2.17 (1 H, ddd, 4.5, 8.6 and 13.9 Hz, 1a-H), 2.28 (1 H, dd, J = 7.5 and 13.2 Hz, 4b-H), 2.39 (1 H, ddd, J = 5.0, 7.7 and 13.9 Hz, 1b-H), 2.56 (1 H, dd, J = 3.6 and 13.2 Hz, 4a-H), 2.82 (1 H, d, J = 12 Hz, 9b-H), 3.94 (1 H, dddd, J = 3.6, 3.8, 7.5 and 7.6 Hz, 3a-H), 4.82 (1 H, d, J = 2.5 Hz, 19-H), 5.05 (1 H, dt, J = 2.5 and 1.2 Hz, 19-H), 6.03 (1 H, d, J = 11.2 Hz, 7-H), 6.25 (1 H, d, J = 11.2 Hz, 6-H) (Ref. 0002)
1H-NMR (d, CDCl3, 300MHz) spectrum (Ref. 0004)
13C-NMR (d, CDCl3, 22.6MHz) 32.1 (1), 35.3 (2), 69.2 (3), 46.0 (4), 135.3 (5), 122.5 (6) 117.8 (7), 142.2 (8), 29.1 (9),* 145.3 (10), 22.4 (11), 40.6 (12), 46.0 (13), 56.5 (14),** 23.7 (15), 27.8 (16),* 56.7 (17),** 11.9 (18), 112.5 (19), 36.2 (20), 18.9 (21), 36.2 (22), 24.0 (23), 39.6 (24), 28.1 (25),* 22.7 (26), 22.9 (27); * and **, the assignments may be interchanged. (Ref. 0003)
m/z 384 (M+), 351, 325, 271, 253, 158, 136, 118; spectrum (Ref. 0015)


Upon sunlight irradiation, 7-dehydrocholesterol (provitamin D3) on the skin isomerizes to previtamin D3 which in turn isomerizes to vitamin D3 at skin temperature. (Ref. 0005/0006)
Synthesis from cholesterol acetate via photochemical isomerization of the corresponding 5,7-diene (provitamin D3) followed by thermal isomerization. (Ref. 0007)
By convergent method from des-AB-cholestan-8-one and A-ring precursor using Wittig-Horner coupling. (Ref. 0286)
Vitamin D3 is hydroxylated by vitamin D 25-hydroxylase (CYP27) in the liver (Ref. 0016/0017) to yield 25-OHD3 and then by 1a-hydroxylase (CYP24B1) (Ref. 0030/0031) in the kidney to afford 1,25-(OH)2D3 (Ref. 0026/0027) , the biologically active form of vitamin D3.


235
3-epivitamin D3 / 3-epicholecalciferol
(5Z,7E)-(3R)-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0238
Sachiko Yamada
3-epi-D3
C27H44O 384.638 Download ChemDraw structure file

p-nitrobenzoate : 117-118 degC (Ref. 0165)
[a]D -0.5 deg (c = 0.9 in C6H6) (Ref. 0165)
lmax (nm) (emax) 264 (18000) (Ref. 0165)
1H-NMR (d, CDCl3) 6.2 (1H, J = 11.2 Hz, 6-H), 6.0 (1H, J = 11.2 Hz, 7-H), 5.0 (1H, 19Z-H), 4.8 (1H, 19E-H), 3.9 (1H, J = 4.1 Hz, 3-H), 0.5 (3H, 18-H) (Ref. 0165)
13C-NMR (d, CDCl3, 20MHz) 32.40 (1), 35.60 (2), 69.70 (3), 46.25 (4), 145.05 (5), 122.25 (6), 117.65 (7), 142.15 (8), 29.10 (9), 135.40 (10), 22.35 (11), 40.65 (12), 45.95 (13), 56.45 (14), 23.70 (15), 27.65 (16), 56.80 (17), 12.00 (18), 112.50 (19) (Ref. 0165)




From vitamin D3 by inverting the configuration at C(3). (Ref. 0165)



236
(5E)-vitamin D3 / (5E)-cholecalciferol / (5E)-calciol
(5E,7E)-(3S)-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0239
Sachiko Yamada
(5E)-D3
C27H44O 384.638 Download ChemDraw structure file

1H-NMR (d, CDCl3, 300MHz) 6.52 (1H, d, J = 11.2 Hz, 6-H), 5.84 (1H, d, J = 11.2 Hz, 7-H), 4.95 (1H, br, 19Z-H), 4.65 (1H, br, 19E-H), 3.86 (1H, dddd, J = 8.5, 8.5, 4.1 and 4.1 Hz, 3a-H), 2.84 (1H, br d, J = 13.8 Hz, 4a-H), 2.84 (1H, d, J = 12.0 Hz, 9b-H), 2.44 (1H, ddd, J = 14.0, 5.0 and 5.0 Hz, 1b-H), 2.21 (1H, dd, J = 13.8 and 8.5 Hz, 4b-H), 2.17 (1H, br d, J = 14.0 Hz, 1a-H), 1.94 (1H, 2a-H), 1.58 (1H, 2b-H), 0.92 (3H, d, J = 6.2 Hz, 21-CH3), 0.87 (6H, d, J = 6.7 Hz, 26-, 27-CH3), 0.57 (3H, s, 18-CH3) (Ref. 0164)
13C-NMR (d, CDCl3, 20MHz) 31.20 (1), 34.80 (2), 69.00 (3), 37.25 (4), 149.25 (5), 121.05 (6), 116.0 (7), 145.55 (8), 29.15 (9), 134.95 (10), 22.40 (11), 40.70 (12), 46.00 (13), 56.70 (14), 23.65 (15), 27.70 (16), 56.85 (17), 12.20 (18), 108.15 (19) (Ref. 0165)




From vitamin D3 via its SO2 adduct: Treatment of D3 with liquid SO2 at its refluxing temperature gives D3-SO2 adduct in quantitative yeild which upon heating in refluxing EtOH in the presence of weak base (such as NaHCO3) gives exclusively 5E-D3. (Ref. 0267/0265)



237
(5E)-3-epivitamin D3 / (5E)-3-epicholecalciferol
(5E,7E)-(3R)-9,10-seco-5,7,10(19)-cholestatrien-3-ol
VVD0240
Sachiko Yamada
(5E)-3-epi-D3
C27H44O 384.638 Download ChemDraw structure file

p-nitrobenzoate : 104-105 degC (Ref. 0165)
[a]D -30.0 deg (c = 0.85 in C6H6) (Ref. 0165)
lmax (nm) (emax) 272 (22000) (Ref. 0165)
1H-NMR (d, CDCl3) 6.5 (1H, J = 11.1 Hz, 6-H), 5.8 (1H, J = 11.1 Hz, 7-H), 4.9 (1H, 19Z-H), 4.6 (1H, 19E-H), 3.8 (1H, J = 4.2 Hz, 3-H), 0.5 (3H, 18-H) (Ref. 0165)
13C-NMR (d, CDCl3, 20MHz) 31.15 (1), 34.75 (2), 68.95 (3), 37.10 (4), 149.20 (5), 121.05 (6), 115.9 (7), 144.65 (8), 29.10 (9), 134.80 (10), 22.35 (11), 40.60 (12), 46.00 (13), 56.60 (14), 23.65 (15), 27.70 (16), 56.75 (17), 12.15 (18), 108.2 (19) (Ref. 0165)




From (5E)-vitamin D3 by inverting the configuration at C(3). (Ref. 0165)



238
previtamin D3 / precholecalciferol / (6Z)-tacalciol
(6Z)-(3S)-9,10-seco-5(10),6,8-cholestatrien-3-ol
VVD0241
Sachiko Yamada
pre-D3
C27H44O 384.638 Download ChemDraw structure file

3:5-Dinitrobenzoate : 104.5-105 degC (Ref. 0008)
[a]d-20 +54 deg (in CHCl3) (Ref. 0008)
lmax (nm) (emax) 260 (9250) (Ref. 0008)









239
tachysterol3
(6E)-(3S)-9,10-seco-5(10),6,8-cholestatrien-3-ol
VVD0242
Sachiko Yamada
tachysterol3
C27H44O 384.638 Download ChemDraw structure file










240
isotachysterol3
(6E)-(3S)-9,10-seco-5(10),6,8(14)-cholestatrien-3-ol
VVD0243
Sachiko Yamada
isotachysterol3
C27H44O 384.638 Download ChemDraw structure file

(EtOH) lmax (nm) 288, 277, 301 (Ref. 0011)
Dinitrobenzoate : 1H=NMR (d, CDCl3, 100MHz) 5.37 (1H, m), 6.54 (1H, d, J = 16 Hz), 6.30 (1H, d, J = 16 Hz), 0.91 (3H, s), 1.90 (3H, s), 0.92 (3H, d, J = 6 Hz), 0.89 (6H, d, J = 6 Hz) (Ref. 0011)
m/z 384 (M+) (Ref. 0011)

RF(TLC) [0.2 nm silicagel plate (Kieselgel G Merk), benzen/acetone] 0.71 (Ref. 0011)
Rrel(GC) [1% SE-30 on GasChrom Q (80-100 mesh), retention time relative to cholestane] 1.47/1.62/2.36/2.60 (Ref. 0011)

Obtained as a minor product by overirradiation of 7-dehydrocholesterol in ethanol or methanol. (Ref. 0011)
Better method of producing this compound is to treat vitamin D3 with Lewis acids as described in vitamin D2 series. (Ref. 0268)



241
(5E)-isovitamin D3 / (5E)-isocholecalciferol
(5E,7E)-(3S)-9,10-seco-1(10),5,7-cholestatrien-3-ol
VVD0244
Sachiko Yamada
(5E)-iso-D3
C27H44O 384.638 Download ChemDraw structure file

(EtOH) lmax (nm) 287, 276, 298 (Ref. 0011)
Dinitrobenzoate : 1H-NMR (d, CDCl3, 100MHz) 5.42 (1H, m), 6.54 (1H, d, J = 12 Hz), 5.91 (1H, d, J = 12 Hz), 0.52 (3H, s), 1.96 (3H, s), 0.93 (3H, d, J = 6 Hz), 0.87 (6H, d, J = 6 Hz) (Ref. 0011)
m/z 384 (M+) (Ref. 0011)

RF(TLC) [0.2 nm silicagel plate (Kieselgel G Merk), benzen/acetone] 0.85 (Ref. 0011)
Rrel(GC) [1% SE-30 on GasChrom Q (80-100 mesh), retention time relative to cholestane] 1.39/1.59/2.27 (Ref. 0011)

Obtained as a minor product by overirradiation of 7-dehydrocholesterol in ethanol or methanol. (Ref. 0011)
Better method of producing this compound is to treat vitamin D3 with Lewis acids as described in vitamin D2 series. (Ref. 0268)



242
provitamin D3 /procholecalciferol / 7-dehydrocholesterol
(3S)-5,7-cholestadien-3-ol
VVD0245
Sachiko Yamada
pro-D3
C27H44O 384.638 Download ChemDraw structure file

126 degC (Ref. 0187)
141.5 degC (Alcohol) (Ref. 0188)
[a]d-25 -50.45 to -49.69 deg (in CHCl3) (Ref. 0188)
lmax (nm) (e) 262.5 pm 5 (7400), 271.0 pm 5 (10400), 281.5 pm 5 (10750), 293.0 pm 5 (6150) (Ref. 0187)
13C-NMR (d, CDCl3, 22.6MHz) 38.5 (1), 32.0 (2), 70.5 (3), 40.8 (4), 141.3 (5), 119.8 (6), 116.5 (7), 140.0 (8), 46.5 (9), 37.2 (10), 21.2 (11), 39.2 (12), 43.1 (13), 54.6 (14), 23.1 (15), 28.1 (16), 56.2 (17), 11.9 (18), 16.4 (19), 36.3 (20), 18.9 (21), 36.3 (22), 24.0 (23), 39.6 (24), 28.1 (25), 22.6 (26), 22.8 (27) (Ref. 0003)



Isolation and identification from pig skin. (Ref. 0190)




243
pyrovitamin D3 / pyrocholecalciferol
(3S)-10a-cholesta-5,7-dien-3-ol
VVD0246
Sachiko Yamada
pyro-D3
C27H44O 384.638 Download ChemDraw structure file

lmax (nm) 274, 285, 296 (Ref. 0009)
1H-NMR (d, CCl4, 100MHz) 0.84 (s, 18-H3), 1.07 (s, 19-H3), 3.95 (narrow m, 3a-H), 5.36 (q, J = 6 Hz, 6-, 7-H2) (Ref. 0009)




From vitamin D3 by heating (110-170 degC) in various organic solvent. (Ref. 0009)



244
isopyrovitamin D3 / isopyrocholecalciferol
(3S)-9b-cholesta-5,7-dien-3-ol
VVD0247
Sachiko Yamada
isopyro-D3
C27H44O 384.638 Download ChemDraw structure file

lmax (nm) 274, 284, 295 (Ref. 0009)
1H-NMR (d, CCl4, 100MHz) 0.85 (s, 18-H3), 1.24 (s, 19-H3), 3.40 (broad m, 3a-H), 5.42 (q, J = 6 Hz, 6-, 7-H2) (Ref. 0009)




From vitamin D3 by heating (110-170 degC) in various organic solvent. (Ref. 0009)



245
toxisterol3 A1
(3S,4S,8S)-4,8-cyclo-9,10-seco-5(10),6-cholestadien-3-ol
VVD0248
Sachiko Yamada
toxisterol3 A1
C27H44O 384.638 Download ChemDraw structure file

94.5-96.5 degC (Ref. 0011/0012)
[a]d-22 -100 deg (in CHCl3) (Ref. 0011/0012)
(EtOH) lmax (nm) (emax) 251 (15000) (Ref. 0011/0012)
(KBr) 3340, 3060, 2950, 2870, 1470, 1380, 1120, 1040, 1020, 990, 930, 860, 760, 500 cm-1 (Ref. 0011)
1H-NMR (d, CDCl3, 100MHz) 3.85 (1 H, dt, J = 3.5, 11 Hz), 6.27 (2 H, s), 0.89 (3 H, s), 1.67 (3 H, d, J = 2 Hz), 0.90 (3 H, d, J = 5 Hz), 0.86 (6 H, d, J = 6 Hz) (Ref. 0011)
13C-NMR (d, CDCl3, 100MHz) 35.2 t (1), 33.8 t (2), 69.8 d (3), 54.0 d (4), 122.6 s (5), 129.2 d (6), 140.6 d (7), 54.0 s (8), 31.4 t (9), 135.7 s (10), 20.1 t (11), 40.0 t (12), 43.9 s (13), 55.7 d (14), 22.3 t (15), 27.2 t (16), 57.0 d (17), 140.0 q (18), 18.4 q (19), 35.4 d (20), 18.4 q (21), 35.9 t (22), 23.7 t (23), 39.5 t (24), 27.9 d (25), 22.5 q (26), 22.8 q (27) (Ref. 0011/0012)
m/z 384 (M+) (Ref. 0011)

RF(TLC) (benzene) 0.57 (Ref. 0011)
Rrel(GC) (retention time relative to cholestane) 1.41 (Ref. 0011)

Obtained as one of overirradiation products of 7-dehydrocholesterol. (Ref. 0011)



246
toxisterol3 A2
(3S,4S,8S)-4,8,-cyclo-9,10-seco-5(10),6-cholestadien-3-ol
VVD0249
Sachiko Yamada
toxisterol3 A2
C27H44O 384.638 Download ChemDraw structure file

[a]d-22 +39 deg (in CHCl3) (Ref. 0011)
(EtOH) lmax (nm) (emax) 251 (15000) (Ref. 0011)
(Neat) 3390, 3060, 2960, 2940, 2870, 1460, 1370, 1120, 1030, 1015, 990, 775, 755, 675 cm-1 (Ref. 0011)
1H-NMR (d, CDCl3, 100MHz) 3.81(1H, dt, J = 3.5, 11 Hz), 6.33 (1H, d, J = 6 Hz), 6.06 (1H, d, J = 6 Hz), 0.90 (3H, s), 1.65 (3H, d, J = 2 Hz), 0.94 (3H, d, J = 6 Hz), 0.87 (6H, d, J = 6 Hz) (Ref. 0011)
13C-NMR (d, CDCl3, 100MHz) 31.4 t (1), 34.0 t (2), 69.8 d (3), 59.7 d (4), 120.5 s (5), 128.6 d (6), 140.8 d (7), 53.2 s (8), 35.7 t (9), 138.1 s (10), 19.6 t (11), 40.2 t (12), 45.0 s (13), 48.0 d (14), 24.2 t (15), 29.8 t (16), 54.3 d (17), 18.2 q (18), 25.5 q (19), 36.2 d (20), 19.4 q (21), 36.8 t (22), 23.8 t (23), 39.5 t (24), 28.0 d (25), 22.5 q (26), 22.8 q (27) (Ref. 0011)
m/z 384 (M+), 253 (base) (Ref. 0011)

RF(TLC) [0.2 nm silicagel plate (Kieselgel G Merk), benzene] 0.31 (Ref. 0011)
Rrel(GC) [1% SE-30 on GasChrom Q (80-100mesh), retention time relative to cholestane] 0.98 (Ref. 0011)

Obtained as one of overirradiation products of 7-dehydrocholesterol. (Ref. 0011)



247
toxisterol3 A3
(3S,4R,8R)-4,8-cyclo-9,10-seco-5(10),6-cholestadien-3-ol
VVD0250
Sachiko Yamada
toxisterol3 A3
C27H44O 384.638 Download ChemDraw structure file

[a]d-22 +128 deg (in CHCl3) (Ref. 0011)
(Diethyl ether) lmax (nm) (emax) 251 (15000) (Ref. 0011)
(Neat) 3430, 3050, 3020, 2930, 2860, 1470, 1380, 1370, 1175, 1090, 1070, 1015, 990, 870, 810, 770 cm-1 (Ref. 0011)
1H-NMR (d, CDCl3, 100MHz) 4.61 (1H, m), 6.14 (1H, d, J = 5.5 Hz), 5.35 (1H, d, J = 5.5 Hz), 0.75 (3H, s), 1.76 (3H, d, J = 1.5 Hz), 0.93 (3H, d, J = 6 Hz), 0.88 (6H, d, J = 6 Hz) (Ref. 0011)
m/z 384 (M+) (Ref. 0011)

RF(TLC) [0.2 nm silicagel plate (Kieselgel G Merk), benzene] 0.31 (Ref. 0011)
Rrel(GC) [1% SE-30 on GasChrom Q (80-100 mesh), retention time relative to cholestane] 1.31 (Ref. 0011)

Obtained as one of overirradiation products of 7-dehydrocholesterol. (Ref. 0011)



248
toxisterol3 C1
(5R,6R,9S,10R)-9(10a_right5),10(9a_right6)abeo-7-cholesten-3b-ol
VVD0251
Sachiko Yamada
toxisterol3 C1
C27H44O 384.638 Download ChemDraw structure file

112 degC (Ref. 0011/0012)
[a]d-22 +141 deg (in CHCl3) (Ref. 0011/0012)
(EtOH) lmax (nm) (emax) 227 (6600) (Ref. 0011/0012)
(KBr) 3380, 3060, 2960, 2940, 2880, 1660, 1470, 1380, 1080, 1045, 1030, 1015, 840 cm-1 (Ref. 0011)
1H-NMR (d, CDCl3, 100MHz) 3.56 (1H, m), 5.02 (1H, d, J = 1.8 Hz), 0.57 (3H, s), 0.81 (3H, s), 0.90 (3H, d, J = 6 Hz), 0.86 (6H, d, J = 6 Hz) (Ref. 0011/0012)
13C-NMR (d, CDCl3, 100MHz) 39.7 t (1), 32.8 t (2), 67.9 d (3), 31.5 t (4), 34.0 s (5), 31.1d (6), 117.7 d (7), 148.1 s (8), 50.2 d (9), 24.5 s (10), 22.3 t (11), 40.5 t (12), 45.4 s (13), 51.6 d (14), 25.5 t (15), 28.6 t (16), 55.6 d (17), 12.2 q (18), 15.2 q (19), 36.3d(20), 18.9 q (21), 36.3 t (22), 23.9 t (23), 39.5 t (24), 28.0 d (25), 22.6 q (26), 22.8 q (27) (Ref. 0011)
m/z 384 (M+), 351 (base) (Ref. 0011)

RF(TLC) [0.2 nm silicagel plate (Kieselgel G Merk), benzene/acetate] 0.63 (Ref. 0011)
Rrel(GC) [1% SE-30 on GasChrom Q (80-100 mesh), retention time relative to cholestane] 1.40 (Ref. 0011)

A major overirradiation products of 7-dehydrocholesterol. (Ref. 0011)



249
toxisterol3 C2
(5S,6S,9S,10S)-9(10a_right5),10(9a_right6)abeo-7-cholesten-3b-ol
VVD0252
Sachiko Yamada
toxisterol3 C2
C27H44O 384.638 Download ChemDraw structure file

102-103 degC (Ref. 0011)
[a]d-22 -69 deg (in CHCl3) (Ref. 0011)
(EtOH) lmax (nm) (emax) 229 (5400) (Ref. 0011)
(KBr) 3360, 3040, 2940, 2860, 1650, 1480, 1390, 1070, 1050, 1020, 825 cm-1 (Ref. 0011)
1H-NMR (d, CDCl3, 100MHz) 3.59 (1H, m), 5.15 (1H, d, J = 2 Hz), 0.73 (3H, s), 0.92 (3H, s), 0.90 (3H, d, J = 6 Hz), 0.86 (6H, d, J = 6 Hz) (Ref. 0011)
13C-NMR (d, CDCl3, 100MHz) 38.4 t (1), 33.6 t (2), 68.9 d (3), 31.7 t (4), 37.7 s (5), 30.1 d (6), 119.7 d (7), 148.6 s (8), 46.4 d (9), 28.3 s (10), 19.3 t (11), 40.8 t (12), 42.6 s (13), 48.0 d (14), 24.0 t (15), 29.1 t (16), 57.2 d (17), 15.5 q (18), 18.4 q (19), 36.0 d (20), 18.9 q (21), 36.0 t (22), 24.0 t (23), 39.5 t (24), 28.0 d (25), 22.5 q (26), 22.8 q (27) (Ref. 0011)
m/z 384 (M+), 351 (Ref. 0011)

RF(TLC) [0.2 nm silicagel plate (Kieselgel G Merk), benzen/acetone] 0.60 (Ref. 0011)
Rrel(GC) [1% SE-30 on GasChrom Q (80-100 mesh), retention time relative to cholestane] 0.95/1.52/1.60 (Ref. 0011)

Obtained as one of overirradiation products of 7-dehydrocholesterol. (Ref. 0011)



250
toxisterol3 D1
(5Z)-(3S)-9,10-seco-5,8,10(19)-cholestatrien-3-ol
VVD0253
Sachiko Yamada
toxisterol3 D1
C27H44O 384.638 Download ChemDraw structure file

Dinitrobenzoate : 108.5-109.5 degC (Ref. 0011/0012)
Dinitrobenzoate : [a]d-22 +37 deg (in CHCl3) (Ref. 0011/0012)
(EtOH) lmax (nm) (emax) 217 (shoulder) (7200) (Ref. 0011/0012)
(Neat) 3340, 3075, 2950, 2930, 2860, 1640, 1460, 1370, 1050, 900 cm-1 (Ref. 0011)
1H-NMR (d, CDCl3, 100MHz) 3.92 (1H, m), 5.34 (1H, t, J = 7 Hz), 2.79 (1H, d, J = 7 Hz), 0.67 (3H, s), 4.73 (3H, d, J = 2 Hz), 4.93 (3H, d, J = 2 Hz), 0.93 (3H, d, J = 7 Hz), 0.86 (6H, d, J = 6 Hz) (Ref. 0011/0012)
m/z 384 (M+) (Ref. 0011)

RF(TLC) [0.2 nm silicagel plate (Kieselgel G Merk), benzen/acetone] 0.71 (Ref. 0011)
Rrel(GC) [1% SE-30 on GasChrom Q (80-100 mesh), retention time relative to cholestane] 1.69/2.58 (Ref. 0011)

Obtained as one of overirradiation products of 7-dehydrocholesterol. (Ref. 0011)



251
toxisterol3 E1
(3S,6R,9R)-9(10a_right6)abeo-5(10),7-cholestadien-3-ol
VVD0254
Sachiko Yamada
toxisterol3 E1
C27H44O 384.638 Download ChemDraw structure file

[a]d-22 +155 deg (in CHCl3) (Ref. 0011)
lmax (nm) (emax) (diethyl ether) no absorption maximum at l > 210 (Ref. 0011)
(KBr) 3420, 2960, 2930, 2870, 1660, 1480, 1390, 1380, 1100, 1040, 810 cm-1 (Ref. 0011)
1H-NMR (d, CDCl3, 100MHz) 3.90 (1H, m), 3.76 (1H, m), 5.57 (1H, s), 0.63 (3H, s), 1.58 (3H, s), 0.94 (3H, d, J = 6 Hz), 0.88 (6H, d, J = 6 Hz) (Ref. 0011)
Dinitrobenzoate : m/z 578 (M+), 366 (base) (Ref. 0011)

RF(TLC) [0.2 nm silicagel plate (Kieselgel G Merk), benzene

Obtained as one of overirradiation products of 7-dehydrocholesterol in ether. (Ref. 0011)



252
(3S,6S)-9,10-seco-5(10),6,7-cholestatrien-3-ol
VVD0255
Sachiko Yamada
C27H44O 384.638 Download ChemDraw structure file

lmax (nm) 230 (Ref. 0013)
1950, 1625 cm -1 (Ref. 0013)
1H-NMR (d, CDCl3, 100MHz) 0.73 (3H, s) 3.90 (1H, m), 6.18 (1H, t, J = 4 Hz) (Ref. 0013)




One of minor irradiation (>250 nm) products of vitamin D3 in ethanol. (Ref. 0013)



253
(3S,6R)-9,10-seco-5(10),6,7-cholestatrien-3-ol
VVD0256
Sachiko Yamada
C27H44O 384.638 Download ChemDraw structure file

lmax (nm) 230 (Ref. 0013)
1950, 1625 cm -1 (Ref. 0013)
1H-NMR (d, CDCl3, 100MHz) 0.65 (3H, s), 0.87 (6H, d, J = 7 Hz), 0.91 (3H, d, J = 7 Hz), 1.74 (3H, s), 3.90 (1H, m), 6.14 (1H, t, J = 4 Hz) (Ref. 0013)




One of minor irradiation (>250 nm) products of vitamin D3 in ethanol. (Ref. 0013)



254
(7E)-(3S,6S)-6,19-cyclo-9,10-seco-5(10),7-cholestadien-3-ol
VVD0257
Sachiko Yamada
C27H44O 384.638 Download ChemDraw structure file

No absorption maxima at l > 200 nm (Ref. 0013)
3,5-Dinitrobenzoate of one of C(6) epimers : 1H-NMR (d, CDCl3, 100MHz) 0.54 (3H, s), 0.86 (6H, d, J = 7 Hz), 0.93 (3H, d, J = 7 Hz), 3.71 (1H, m), 4.91 (1H, d, J = 9 Hz), 5.30 (1H, m) (Ref. 0013)




One of minor irradiation (>250 nm) products of vitamin D3 in ethanol. (Ref. 0013)



255
1a-hydroxyvitamin D3 / 1a-hydroxycholecalciferol
(5Z,7E)-(1S,3R)-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0258
Sachiko Yamada
1a-OHD3
C27H44O2 400.637 Download ChemDraw structure file
Intestinal calcium transport and bone mineral mobilization response to 1a-OH-D3 and 25-OH-D3 in anephric rats. : Table(Ref. 0168)
Intestinal calcium transport and bone calcium mobilization response of rats to 1a-OH-D3. Results are means of six rats ; S.E., standard error. : Table (Ref. 0172)
HL-60 human promyelocytes differentiation : ED50 in nitro blue tetrazplium reduction, phagocytic activity, and nonspecific acid esterase activity are 9.3 times 10-7 M, 1.0 times 10-6 M and 1.0 times 10-6 M, respectively, when 1,25-(OH)2D3 shows the respective ED50 values of 1.0 times 10-8 M, 1.0 times 10-8 M and 1.1 times 10-8 M, respectively. (Ref. 0228)
Treatment of psoriasis : A case of psoriasis with senile osteoporosis is reported in which skin lesions were cured two and half months after the start of administration of 0.75 mg/day of 1a-OHD3. (Ref. 0248)
134-136 degC (Ref. 0167)
[a]d-25 +28.0 deg (c = 0.6 in Et2O) (Ref. 0167)
(Et2O) lmax (nm) (emax) 264-265 (18000) (Ref. 0167)
(CHCl3) 895m, 912m, 952m, 1040s, 1645m, 3450m, 3600s cm-1 (Ref. 0167)
1H-NMR (d, CDCl3) 3.58 (1H, d, J = 12 Hz, 6- or 7-H), 3.99 (1H, d, J = 12 Hz, 6- or 7-H), 4.66 (1H, m, 19-H), 4.99 (1H, m, 19-H), 5.45-6.05 (2H, m, >CH-O), 9.12 (9H, d, J = 6 Hz, MeCH<), 9.45 (3H, s, 18-H) (Ref. 0167)
m/z 382 (5.2%), 364 (16.2%), 149 (26.0%), 134 (6.1%), 128 (30.4%), 121 (67.5%), 119 (32.0%), 95 (49.4%), 83 (50.5%), 81 (59%), 71 (58.5%), 69 (76.3%), 57 (100%) (Ref. 0167)



From cholesterol. (Ref. 0035)
From 1,4,6-cholestatrien-3-one via its regio- and stereoselective epoxidation followed by deconjugative reduction to yield 1a-hydroxycholesterol as the key step. (Ref. 0166)
Total synthesis from 9a-chloro-des-AB-cholestan-8-one and optically active A-ring synthon having C(6)-C(7) linker part as ethyl group. (Ref. 0167)
From 1,4-cholestadien-3-one via steps of deconjugation followed by reduction, hydroboration, bromination, dehydrobromination, and photochemical and thermal isomerizations. (Ref. 0168)
Synthesis of 1a-hydroxyprovitamin D3 from 1,4,6-cholestatrien-3-one via steps of deconjugation followed by reduction, protection of 5,7-diene, epoxidation, and reduction. (Ref. 0169/0170)
From vitamin D3 via SeO2 oxidation of 3,5-cyclo-vitamin D derivative. (Ref. 0171)



256
1a-hydroxy-3-epivitamin D3 / 1a-hydroxy-3-epicholecalciferol
(5Z,7E)-(1S,3S)-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0259
Sachiko Yamada
1a-OH-3-epi-D3
C27H44O2 400.637 Download ChemDraw structure file
Relative Efficacy of 1,3-diol Stereoisomers in Competing with 1,25-(OH)2-[26 ,27-3H]D3 for Binding to The Receptor Protein. (Ref. 0175)
lmax (nm) 263 (Ref. 0175)
1H-NMR (d, CDCl 3) 0.54 (3H, s, 18-H3), 4.05 (1H, m, 3-H), 4.30 (1H, m, 1-H), 5.00 [1H, m, 19(Z)-H], 5.30 [1H, m, 19(E)-H], 6.02 (1H, d, J = 11.4 Hz, 7-H), 6.44 (1H, d, J = 11.4 Hz, 6-H) (Ref. 0175)
m/z 400 (M+, 20), 382 (35), 364 (15), 152 (100), 134 (90) (Ref. 0175)



From 3-epivitamin D3 : SeO2 oxidation of its 3,5-cyclovitamin D derivative gave 1-oxo-derivative as a minor product which by LiAlH4 gave 1a-hydroxylated cyclovitamin D as the major product. 1a-Hydroxy-3-epivitamin D3 was obtained from this compound by cycloreversion followed by hydrolysis. (Ref. 0175)
From 1a-hydroxycholesterol via the steps of the inversion of the configuration at C(3) by Mitsunobu method, bromination, dehydrobromination and photochemical followed by thermal isomerization. (Ref. 0177)



257
(5E)-1a-hydroxyvitamin D3 / (5E)-1a-hydroxycholecalciferol
(5E,7E)-(1S,3R)-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0260
Sachiko Yamada
(5E)-1a-OHD3
C27H44O2 400.637 Download ChemDraw structure file
Relative Efficacy of 1,3-diol Stereoisomers in Competing with 1,25-(OH)2-[26 ,27-3H]D3 for Binding to The Receptor Protein. Table (Ref. 0175)
lmax (nm) 273 (Ref. 0175)
1H-NMR (d, CDCl3) 0.57 (3H, s, 18-H3), 4.24 (1H, m, 3-H), 4.50 (1H, m, 1-H), 4.97 [1H, m, 19(Z)-H], 5.12 [1H, m, 19(E)-H], 5.89 (1H, d, J = 11.6 Hz, 7-H), 6.58 (1H, d, J = 11.6 Hz, 6-H) (Ref. 0175)
m/z 400 (M+, 15), 382 (5), 364 (1), 152 (40), 134 (100) (Ref. 0175)



From vitamin D3 via SeO2 oxidation of its 3,5-cyclovitamin D derivative as the key step. Cycloreversion followed by hydrolysis of 1a-hydroxylated cyclovitamin D gave (5Z)- and (5E)-1ahydroxyvitamin D3 in about 2 : 1 ratio. (Ref. 0175)



258
(5E)-1a-hydroxy-3-epivitamin D3 / (5E)-1a-hydroxy-3-epicholecalciferol
(5E,7E)-(1S,3S)-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0261
Sachiko Yamada
(5E)-1a-OH-3-epi-D3
C27H44O2 400.637 Download ChemDraw structure file
Relative Efficacy of 1,3-diol Stereoisomers in Competing with 1,25-(OH)2-[26 ,27-3H]D3 for Binding to The Receptor Protein. Table (Ref. 0175)
lmax (nm) 271 (Ref. 0175)
1H-NMR (d, CDCl3) 0.57 (3H, s, 18-H3), 4.13 (1H, m, 3-H), 4.38 (1H, m, 1-H), 4.96 [1H, m, 19(Z)-H], 5.12 [1H, m, 19(E)-H], 5.90 (1H, d, J = 11.4 Hz, 7-H), 6.64 (1H, d, J = 11.4 Hz, 6-H) (Ref. 0175)
m/z 400 (M+, 20), 382 (5), 364 (1), 152 (100), 134 (70) (Ref. 0175)



From 3-epivitamin D3 : SeO2 oxidation of its 3,5-cyclovitamin D derivative gave 1-oxo-derivative as a minor product which by LiAlH4 gave 1a-hydroxylated cyclovitamin D as the major product. Cycloreversion followed by hydrolysis gave (5Z)- and (5E)-isomers of 1a-hydroxy-3-epivitamin D3 in about 2 : 1 ratio. (Ref. 0175)



259
1b-hydroxyvitamin D3 / 1b-hydroxycholecalciferol
(5Z,7E)-(1R,3R)-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0262
Sachiko Yamada
1b-OHD3
C27H44O2 400.637 Download ChemDraw structure file
Binding affinity for intestinal vitamin D receptor was 1/1.65 times105 relative to 1,25-(OH)2D3. (Ref. 0176)
(EtOH) lmax (nm) (emax) 263 (17000) (Ref. 0176)
1H-NMR (d, CDCl3, 270MHz) 0.55 (3H, s, 13-Me), 0.87 (6H, d, 25-Me2), 4.11 (1H, narrow m, 3-H), 4.37 (1H, narrow m, 1-H), 5.01 [1H, d, J = 1.9 Hz, 19(Z)-H], 5.29 (1H, d, J = 1.9 Hz, 19(E)-H], 6.46 and 6.06 (2H, AB q, J = 11.7 Hz, 6- and 7-H) (Ref. 0176)
m/z 400 (M+, 18%), 382 (35%), 264 (25%), 152 (100%), 134 (90%) (Ref. 0176)



From 1a-hydroxyvitamin D3 : Selective oxidation of the 1-hydroxyl group yielded 1-oxoprevitamin D3 which by LiAlH4 reduction gave 1b-hydroxyvitamin D3 and its 1a-isomer in 4 : 1 ratio. (Ref. 0176/0178)



260
1b-hydroxy-3-epivitamin D3 / 1b-hydroxy-3-epicholecalciferol
(5Z,7E)-(1R,3S)-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0263
Sachiko Yamada
1b-OH-3-epi-D3
C27H44O2 400.637 Download ChemDraw structure file
Relative Efficacy of 1,3-diol Stereoisomers in Competing with 1,25-(OH)2-[26 ,27-3H]D3 for Binding to The Receptor Protein. : Table (Ref. 0175)
lmax (nm) 264 (Ref. 0175)
1H-NMR (d, CDCl3) 0.55 (3H, m, 18-H3), 4.21 (1H, m, 3-H), 4.44 (1H, m, 1-H), 5.01 [1H, m, 19(Z)-H], 5.32 [1H, m, 19(E)-H], 6.00 (1H, d, J = 11.4 Hz, 7-H), 6.39 (1H, d, J = 11.4 Hz, 6-H) (Ref. 0175)
m/z 400 (M+, 25), 382 (20), 364 (10), 152 (55), 134 (100) (Ref. 0175)



From 3-epivitamin D3 via SeO2 oxidation of its 3,5-cyclovitamin D derivative as the key step. (Ref. 0175)



261
(5E)-1b-hydroxyvitamin D3 / (5E)-1b-hydroxycholecalciferol
(5E,7E)-(1R,3R)-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0264
Sachiko Yamada
(5E)-1b-OHD3
C27H44O2 400.637 Download ChemDraw structure file
Relative Efficacy of 1,3-diol Stereoisomers in Competing with 1,25-(OH)2-[26 ,27-3H]D3 for Binding to The Receptor Protein. : Table (Ref. 0175)
lmax (nm) 271 (Ref. 0175)
1H-NMR (d, CDCl3) 0.57 (3H, s, 18-H3), 4.11 (1H, m, 3-H), 4.38 (1H, m, 1-H), 4.96 [1H, m, 19(Z)-H], 5.12 [1H, m, 19(E)-H], 5.90 (1H, d, J = 11.4 Hz, 7-H), 6.64 (1H, d, J = 11.4 Hz, 6-H) (Ref. 0175)
m/z 400 (M+, 15), 382 (5), 364 (2), 152 (100), 134 (80) (Ref. 0175)



From 3-epivitamin D3 : SeO2 oxidation of its 3,5-cyclovitamin D derivative gave 1-oxo-derivative as a minor product which by LiAlH4 gave 1b-hydroxylated cyclovitamin D as the major product. Cycloreversion followed by hydrolysis gave (5Z)- and (5E)-isomers of 1b-hydroxy-3-epivitamin D3 in about 2 : 1 ratio. (Ref. 0175)



262
(5E)-1b-hydroxy-3-epivitamin D3 / (5E)-1b-hydroxy-3-epicholecalciferol
(5E,7E)-(1R,3S)-9,10-seco-5,7,10(19)-cholestatriene-1,3-diol
VVD0265
Sachiko Yamada
(5E)-1b-OH-3-epi-D3
C27H44O2 400.637 Download ChemDraw structure file
Relative Efficacy of 1,3-diol Stereoisomers in Competing with 1,25-(OH)2-[26 ,27-3H]D3 for Binding to The Receptor Protein.(Ref. 0175)
lmax (nm) 273 (Ref. 0175)
1H-NMR (d, CDCl3) 0.57 (3H, m, 18-H3), 4.25 (1H, m, 3-H), 4.50 (1H, m, 1-H), 4.97 [1H, m, 19(Z)-H], 5.12 [1H, m, 19(E)-H], 5.88 (1H, d, J = 11.4 Hz, 7-H), 6.58 (1H, d, J = 11.4 Hz, 6-H) (Ref. 0175)
m/z 400 (M+, 10), 382 (6), 364 (1), 152 (35), 134 (100) (Ref. 0175)



From 3-epivitamin D3 via SeO2 oxidation of its 3,5-cyclovitamin D derivative as the key step. (Ref. 0175)



263
2a-hydroxyvitamin D3 / 2a-hydroxycholecalciferol
(5Z,7E)-(2R,3R)-9,10-seco-5,7,10(19)-cholestatriene-2,3-diol
VVD0266
Sachiko Yamada
2a-OHD3
C27H44O2 400.637 Download ChemDraw structure file










264
2b-hydroxyvitamin D3 / 2b-hydroxycholecalciferol
(5Z,7E)-(2S,3R)-9,10-seco-5,7,10(19)-cholestatriene-2,3-diol
VVD0267
Sachiko Yamada
2b-OHD3
C27H44O2 400.637 Download ChemDraw structure file










265
1a,25-dihydroxy-3-deoxyvitamin D3 / 1a,25-dihydroxy-3-deoxycholecalciferol
(5Z,7E)-(1S)-9,10-seco-5,7,10(19)-cholestatriene-1,25-diol
VVD0268
Sachiko Yamada
C27H44O2 400.637 Download ChemDraw structure file
Affinity for chick intestinal receptor : 1/8 as effective as 1,25-(OH)2D3. (Ref. 0310)





From 1a,25-dihydroxycholesterol via reductive deoxygenation of 3-tosyloxy group followed by conventional photochemical transformation. (Ref. 0310)



266
astrogorgiadiol B
(8S,9R)-9,10-seco-1,3,5(10)-cholestatriene-3,9-diol
VVD0269
Sachiko Yamada
astrogorgiadiol B
C27H44O2 400.637 Download ChemDraw structure file
Inhibit cell division in fertilized starfish eggs. (Ref. 0317)
[a]D -4.6 deg (c = 0.2 in CHCl3) (Ref. 0316)
1H-NMR (d, CDCl3, 400MHz) 0.69 (3H, s, 18-CH3), 0.86 (3H, d, J = 6.6 Hz, 26- or 27-CH3), 0.87 (3H, d, J = 6.6 Hz, 26- or 27-CH3), 0.92 (3H, d, J = 6.5 Hz, 21-CH3), 2.22 (3H, s, 19-CH3), 2.42 (1H, ddd, J = 13.5, 10.7, 3.4 Hz, 6-H), 2.69 (1H, ddd, J = 13.5, 11.1, 3.4 Hz, 6'-H), 4.05 (1H, bs, 9-H), 6.57 (1H, dd, J = 8.1, 2.7 Hz, 2-H), 6.65 (1H, d, J = 2.7 Hz, 4-H), 6.97 (1H, d, J = 8.1 Hz, 1-H) (Ref. 0316)
13C-NMR (d, CDCl3, 100MHz) 11.5, 18.4, 18.5, 22.5, 22.8, 23.8, 25.1, 27.6, 28.0, 29.0, 31.0, 35.6, 35.9, 38.3, 38.5, 39.4, 42.8, 50.4, 55.0, 55.2, 112.5, 115.7, 128.0, 131.0, 142.5, 153.7, 213.4 (Ref. 0316)
m/z 400 (M+), 382, 367 (Ref. 0316)


Isolated from a gorgonian of the genus Astrogorgia. (Ref. 0319)
By the coupling of upper-half fragment derived from Grundmann's ketone with lower-half fragment of benzyl iodide derivative. (Ref. 0316)



267
(22S)-22-hydroxyvitamin D3 / (22S)-22-hydroxycholecalciferol
(5Z,7E)-(3S,22S)-9,10-seco-5,7,10(19)-cholestatriene-3,22-diol
VVD0270
Sachiko Yamada
22S-OHD3
C27H44O2 400.637 Download ChemDraw structure file
Displayed no vitamin D agonist activity in the intestine or in bone in vivo and did not block the activity of D3 or 25-OHD3. Affinity for chick intestinal receptor : B-50 (molar concentration sufficient to displace 50% of specifically bound radiolabeled 1,25-(OH)2D3 from the chick intestinal receptor), > 1.19 times 10-4 M (B-50 value for 1,25-(OH)2D3 and 25-OHD3, 2.11 times 10-10 M and 1.4 times 10-7 M, respectively). (Ref. 0311)
(EtOH) lmax (nm) 265, lmin (nm) 227 (Ref. 0311)
1H-NMR (d, CDCl3) 3.67 (1H, m, 22-H), 4.04 (1H, m, 3a-H), 4.82 (1H, d, J = 2.24 Hz, 19-H), 5.06 (1H, d, J = 2.24 Hz, 19-H), 6.03 and 6.28 (each 1H, d, J = 11.2 Hz, 6- and 7-H) (Ref. 0311)
m/z 400 (M+, 43.44), 382 (M+-H2O, 12.56), 367 (M+-H2O-CH3, 42.64), 349 (M+-2H2O-CH3, 11.43), 271 (M+-side chain, 11.77), 254 (M+-side chain-H2O, 22.41), 136 (ring A plus C-6 and C-7, 98.56), 118 (136-H2O, 88.76) (Ref. 0311)



From 23,24-dinor-5-cholenoic acid via the Grignard reaction of the corresponding C-22 aldehyde with side chain fragment as key step. (Ref. 0311)



268
(24R)-24-hydroxyvitamin D3 / (24R)-24-hydroxycholecalciferol
(5Z,7E)-(3S,24R)-9,10-seco-5,7,10(19)-cholestatriene-3,24-diol
VVD0271
Sachiko Yamada
24R-OHD3
C27H44O2 400.637 Download ChemDraw structure file


m/z 400 (M+), 271, 253, 136, 118; spectrum(Ref. 0133)
Bis (trimethylsilyl) ether : m/z 544 (M+), 544, 501, 454, 208, 145, 118; spectrum(Ref. 0133)


Isolation and identification: From the blood plasma of chickens given large doses of vitamin D3. (Ref. 0133)
Synthesis of epimeric mixture at C(24) of 24,25-(OH)2D3 from 3b-acetoxy-27-nor-5-cholesten-25-one. (Ref. 0133)



269
(24S)-24-hydroxyvitamin D3 / (24S)-24-hydroxycholecalciferol
(5Z,7E)-(3S,24S)-9,10-seco-5,7,10(19)-cholestatriene-3,24-diol
VVD0272
Sachiko Yamada
24S-OHD3
C27H44O2 400.637 Download ChemDraw structure file










270
25-hydroxyvitamin D3 / 25-hydroxycholecalciferol / calcidiol
(5Z,7E)-(3S)-9,10-seco-5,7,10(19)-cholestatriene-3,25-diol
VVD0273
Sachiko Yamada
25-OHD3
C27H44O2 400.637 Download ChemDraw structure file
Activities of vitamin D3 in intestinal calcium transport and bone calcium mobilization were compared with those of 25-OHD3: Tables (Ref. 0014)
Antirachitic Activity (IU/mg)(the standard line test assay for vitamin D activity as described in The United States Pharmacopoeia): 25-OHD3 56 pm 6 ; vitamin D3, 40 pm 4. (Ref. 0019)
HL-60 human promyelocytes differentiation: ED50 in nitro blue tetrazplium reduction, phagocytic activity, and nonspecific acid esterase activity are 8.4 times 10-7 M, 8.0 times 10-7 M and 8.0 times 10-7 M, respectively, when 1,25-(OH)2D3 shows the respective ED50 values of 1.0 times 10-8 M, 1.0 times 10-8 M and 1.1 times 10-8 M, respectively. (Ref. 0228)
96-106 degC (Ref. 0262)
95-100 degC (Ref. 0298)
[a]d-25 +88.1 deg (c = 0.5 in EtOH) (Ref. 0262)
(EtOH) lmax (nm) (e) 265 (18000) (Ref. 0014)
lmax (nm) (e) 265 (17700) (Ref. 0298)
(KBr) 3500, 3360, 3080, 3030, 1650, 1635, 1050, 900, 880, 860, 765 cm-1 (Ref. 0298)
1H-NMR (d, CDCl3, 100MHz) 0.54 (3H, s), 0.90 (3H, d, J = 8 Hz), 1.22 (6H, s), 4.80 and 5.00 (each 1H, s), 5.97 and 6.25 (each 1H, d, J = 12 Hz) (Ref. 0014)
1H-NMR (d) 0.54 (3H, s, 18-CH3), 0.93 (3H, d, J = 5 cps, 21-CH3), 1.21 (6H, s, 26- and 27-CH3), 3.90 (1H, bm, 3-CH), 4.81 and 5.04 (2H, 2d, =CH2), 6.02 (1H, d, J = 12 cps, 7-CH), 6.21 (1H, d, J = 12 cps, 6-CH) (Ref. 0298)
m/z 400, 367, 341, 271, 253, 158, 136, 118; spectrum(Ref. 0014/0015)
X-ray crystal structure (Ref. 0274)
HPLC: (Ref. 0023)
Isolation and identification: from plasma of pigs (Ref. 0015/0021) ; from human plasma. (Ref. 0019)
Concentration in human plasma : 10-40 ng/ml (Ref. 0020)
Synthesis from 25-hydroxycholesterol acetate and 3b-acetoxy-27-nor-cholest-5-en-25-one by standard photochemical method via 5,7-cholestadiene-3b,25-diol. (Ref. 0014)
8b,25-Dihydroxy-3,5-cyclovitamin D derivative was synthesized in a convergent method from 25-hydroxylated Grundman's ketone and A-ring precursor and the title compound was prepared from the 3,5-cyclovitamin D by cycloreversion followed by photochemical isomerization. (Ref. 0262)
Biosynthesis: Hydroxylation of D3 by vitamin D 25-hydroxylase (CYP27) in the liver. (Ref. 0016/0017)
Further metabolism : 1a-Hydroxylation in the kidney to give 1a,25-(OH)2D3 under vitamin D deficient conditions. (Ref. 0017/0018/0022)
24-Hydroxylation to give 24R,25-(OH)2D3 in tissues possessing vitamin D receptor under vitamin D supplemented conditions. (Ref. 0017/0018)
26-Hydroxylation to give 25,26-(OH)2D3. (Ref. 0126)


271
25-hydroxy-14-epivitamin D3 / 25-hydroxy-14-epicholecalciferol
(5Z,7E)-(3S)-9,10-seco-5,7,10(19)-cholestatriene-3,25-diol
VVD0274
Sachiko Yamada
14-epi-25-OHD3
C27H44O2 400.637 Download ChemDraw structure file
Biological activity (% of 1,25-(OH)2D3 effect) : Affinity for chick intestinal receptor, 0.08% ; Affinity for human vitamin D binding protein, 3450% ; Intestinal calcium absorption in vitamin D-deficient chicks, < 0.1% ; Bone calcium mobilization in vitamin D-deficient chicks, < 1%. (Ref. 0314)
(95% EtOH) lmax (nm) (e) 264 (18100), lmin (nm) (emin) 230 (11000) (Ref. 0314)