3β-(Benzoyloxy)-4,4-dimethyl-5α-cholest-7-ene-14α-carbonitrile | 136209-53-5

• 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)-4,4-dimethyl-5α-cholest-7-ene-14α-carbonitrile
• 英文别名: 3β-benzoyloxy-14α-cyano-4,4-dimethyl-5α-cholest-7-ene；3beta-Benzoyloxy-14alpha-cyano-4,4-dimethyl-5alpha-cholest-7-ene；[(3S,5R,9R,10R,13R,14S,17R)-14-cyano-4,4,10,13-tetramethyl-17-[(2R)-6-methylheptan-2-yl]-2,3,5,6,9,11,12,15,16,17-decahydro-1H-cyclopenta[a]phenanthren-3-yl] benzoate
• CAS: 136209-53-5
• 化学式: C₃₇H₅₃NO₂
• 分子量: 543.833
• InChiKey: WUQNBTUTNSATRZ-OYOZOGNYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.6
• 重原子数：
  40
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3β-(Benzoyloxy)-4,4-dimethyl-5α-cholest-7-ene-14α-carbonitrile 在 硫酸 、 二异丁基氢化铝 作用下， 生成 3β-hydroxylanost-7-en-32-al
  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：

  3β-(Benzoyloxy)-4,4-dimethyl-7-oxo-5α-cholestane-14α-carbonitrile 在 吡啶 、 sodium tetrahydroborate 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 3.5h， 生成 3β-(Benzoyloxy)-4,4-dimethyl-5α-cholest-7-ene-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

• Steroidal 14.alpha.-carboxy-alkyl derivatives as regulators of HMG-COA
  申请人：SmithKline Beecham Corporation

  公开号：US05023250A1

  公开（公告）日：1991-06-11

  New 14.alpha.-carboxyalkyl sterols are regulators of HMG-CoA reductase and inhibitors of mammalian 14.alpha.-methyl demethylase and are useful in lowering serum cholesterol levels and treating fungal infections.

  新的14.alpha.-羧基烷基甾醇是HMG-CoA还原酶的调节剂，是哺乳动物14.alpha.-甲基去甲基酶的抑制剂，可用于降低血清胆固醇水平和治疗真菌感染。
• US5023250A
  申请人：——

  公开号：US5023250A

  公开（公告）日：1991-06-11