Benzoic acid (3S,5R,8R,9S,10S,13R,14R,17R)-14-cyano-10,13-dimethyl-7-oxo-17-((E)-(1R,4R)-1,4,5-trimethyl-hex-2-enyl)-hexadecahydro-cyclopenta[a]phenanthren-3-yl ester | 136209-58-0

• 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: Benzoic acid (3S,5R,8R,9S,10S,13R,14R,17R)-14-cyano-10,13-dimethyl-7-oxo-17-((E)-(1R,4R)-1,4,5-trimethyl-hex-2-enyl)-hexadecahydro-cyclopenta[a]phenanthren-3-yl ester
• CAS: 136209-58-0
• 化学式: C₃₆H₄₉NO₃
• 分子量: 543.79
• InChiKey: ZAXVYPOZZSLBFB-MKPFHSPRSA-N

物化性质

• 沸点：
  634.6±55.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.43
• 重原子数：
  40.0
• 可旋转键数：
  6.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  67.16
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  Benzoic acid (3S,5R,8R,9S,10S,13R,14R,17R)-14-cyano-10,13-dimethyl-7-oxo-17-((E)-(1R,4R)-1,4,5-trimethyl-hex-2-enyl)-hexadecahydro-cyclopenta[a]phenanthren-3-yl ester 在 palladium on activated charcoal 吡啶 、 盐酸 、 sodium tetrahydroborate 、 氢气 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙酸乙酯 、 甲苯 为溶剂， 反应 6.83h， 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 (3S,5R,8R,9R,10S,13R,14S,17R)-10,13-dimethyl-7-oxo-17-((E)-(1R,4R)-1,4,5-trimethyl-hex-2-enyl)-tetradecahydro-20-oxa-cyclopropa[8,14]cyclopenta[a]phenanthren-3-yl ester 在 溶剂黄146 、 锌 作用下， 以 甲苯 为溶剂， 反应 0.5h， 生成 Benzoic acid (3S,5R,8R,9S,10S,13R,14R,17R)-14-cyano-10,13-dimethyl-7-oxo-17-((E)-(1R,4R)-1,4,5-trimethyl-hex-2-enyl)-hexadecahydro-cyclopenta[a]phenanthren-3-yl ester
  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