3β-(Benzoyloxy)-24-oxo-5α-cholesta-7,22-diene-14α-carbonitrile | 141292-16-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: 3β-(Benzoyloxy)-24-oxo-5α-cholesta-7,22-diene-14α-carbonitrile
• 英文别名: [(3S,5S,9R,10S,13R,14S,17R)-14-cyano-10,13-dimethyl-17-[(E,2R)-6-methyl-5-oxohept-3-en-2-yl]-1,2,3,4,5,6,9,11,12,15,16,17-dodecahydrocyclopenta[a]phenanthren-3-yl] benzoate
• CAS: 141292-16-2
• 化学式: C₃₅H₄₅NO₃
• 分子量: 527.747
• InChiKey: YPTXHSSXMUPUTQ-HNKBNOEHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  39
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  67.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3β-(Benzoyloxy)-24-oxo-5α-cholesta-7,22-diene-14α-carbonitrile 在 palladium on activated charcoal 盐酸 、 氢气 作用下， 以 四氢呋喃 、 乙酸乙酯 为溶剂， 反应 6.25h， 生成 3α-Hydroxy-5α-ergosta-7,24(28)-diene-14α-carbonitrile
  参考文献：
  名称：

  Regioselective synthesis of .DELTA.6-, .DELTA.7-, and .DELTA.8-14.alpha.-cyanosterol derivatives: versatile precursors to 14.alpha.-demethylase inhibitors

  摘要：

  The efficient preparation of 3-beta-(benzoyloxy)-4,4-dimethyl-5-alpha-cholest-8(14)-en-7-one (4a) and 3-beta-benyloxy)-5-alpha-ergost-8(14)-en-7-one (4b) and their conversion to DELTA-6-, DELTA-7- or DELTA-8-14-alpha-functionalized sterols is reported. The alkylaluminum-mediated 1,4-addition of HCN (Nagata reaction) to enones 4a,b is used to introduce the 14-alpha-substituent. Reduction of these conjugate addition products (5a,b) affords the 7-alpha-hydroxysterols (6a,b). The dehydration of 6a with Martin sulfurane reagent regioselectively produces the DELTA-6-14-alpha-cyanosterol 8. Alternatively, mesylation of 6a and elimination affords a mixture of DELTA-7:DELTA-6-sterols (3:1) from which the DELTA-6-sterol is removed by selective ozonolytic degradation. The ozonolytic stability of the DELTA-7-14-alpha-cyanosterols is also exploited in the preparation of 14-alpha-cyanosterols possessing modified side chains. Ozonolysis of 3-beta-(benzoyloxy)-5-alpha-ergost-7,22-diene-14-alpha-carbonitrile (9b) gave 18, which is used to prepare compounds containing the "24 methenyl" (21) and "lanosterol" (23) side chains. The trapping of the intermediate aluminum enolate formed in the hydrocyanation of 4a gives an 8-beta-bromosterol 13. Dehydrobromination of 13 provides a novel regioselective synthesis of the difficult to prepare DELTA-8-14-alpha-functionalized sterol 14.

  DOI：

  10.1021/jo00038a024
• 作为产物：
  描述：

  benzoic acid-(5α-ergostadien-(7.22t)-yl-(3β)-ester) 在 吡啶 、 chromium(VI) oxide 、 sodium tetrahydroborate 、 selenium(IV) oxide 、 水 、 对甲苯磺酸 、 溶剂黄146 、 锌 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 1.08h， 生成 3β-(Benzoyloxy)-24-oxo-5α-cholesta-7,22-diene-14α-carbonitrile
  参考文献：
  名称：

  Regioselective synthesis of .DELTA.6-, .DELTA.7-, and .DELTA.8-14.alpha.-cyanosterol derivatives: versatile precursors to 14.alpha.-demethylase inhibitors

  摘要：

  The efficient preparation of 3-beta-(benzoyloxy)-4,4-dimethyl-5-alpha-cholest-8(14)-en-7-one (4a) and 3-beta-benyloxy)-5-alpha-ergost-8(14)-en-7-one (4b) and their conversion to DELTA-6-, DELTA-7- or DELTA-8-14-alpha-functionalized sterols is reported. The alkylaluminum-mediated 1,4-addition of HCN (Nagata reaction) to enones 4a,b is used to introduce the 14-alpha-substituent. Reduction of these conjugate addition products (5a,b) affords the 7-alpha-hydroxysterols (6a,b). The dehydration of 6a with Martin sulfurane reagent regioselectively produces the DELTA-6-14-alpha-cyanosterol 8. Alternatively, mesylation of 6a and elimination affords a mixture of DELTA-7:DELTA-6-sterols (3:1) from which the DELTA-6-sterol is removed by selective ozonolytic degradation. The ozonolytic stability of the DELTA-7-14-alpha-cyanosterols is also exploited in the preparation of 14-alpha-cyanosterols possessing modified side chains. Ozonolysis of 3-beta-(benzoyloxy)-5-alpha-ergost-7,22-diene-14-alpha-carbonitrile (9b) gave 18, which is used to prepare compounds containing the "24 methenyl" (21) and "lanosterol" (23) side chains. The trapping of the intermediate aluminum enolate formed in the hydrocyanation of 4a gives an 8-beta-bromosterol 13. Dehydrobromination of 13 provides a novel regioselective synthesis of the difficult to prepare DELTA-8-14-alpha-functionalized sterol 14.

  DOI：

  10.1021/jo00038a024

文献信息

• US5023250A
  申请人：——

  公开号：US5023250A

  公开（公告）日：1991-06-11
• Regioselective synthesis of .DELTA.6-, .DELTA.7-, and .DELTA.8-14.alpha.-cyanosterol derivatives: versatile precursors to 14.alpha.-demethylase inhibitors
  作者：Timothy F. Gallagher、Jerry L. Adams

  DOI：10.1021/jo00038a024

  日期：1992.6

  The efficient preparation of 3-beta-(benzoyloxy)-4,4-dimethyl-5-alpha-cholest-8(14)-en-7-one (4a) and 3-beta-benyloxy)-5-alpha-ergost-8(14)-en-7-one (4b) and their conversion to DELTA-6-, DELTA-7- or DELTA-8-14-alpha-functionalized sterols is reported. The alkylaluminum-mediated 1,4-addition of HCN (Nagata reaction) to enones 4a,b is used to introduce the 14-alpha-substituent. Reduction of these conjugate addition products (5a,b) affords the 7-alpha-hydroxysterols (6a,b). The dehydration of 6a with Martin sulfurane reagent regioselectively produces the DELTA-6-14-alpha-cyanosterol 8. Alternatively, mesylation of 6a and elimination affords a mixture of DELTA-7:DELTA-6-sterols (3:1) from which the DELTA-6-sterol is removed by selective ozonolytic degradation. The ozonolytic stability of the DELTA-7-14-alpha-cyanosterols is also exploited in the preparation of 14-alpha-cyanosterols possessing modified side chains. Ozonolysis of 3-beta-(benzoyloxy)-5-alpha-ergost-7,22-diene-14-alpha-carbonitrile (9b) gave 18, which is used to prepare compounds containing the "24 methenyl" (21) and "lanosterol" (23) side chains. The trapping of the intermediate aluminum enolate formed in the hydrocyanation of 4a gives an 8-beta-bromosterol 13. Dehydrobromination of 13 provides a novel regioselective synthesis of the difficult to prepare DELTA-8-14-alpha-functionalized sterol 14.