tert-Butyl-[(3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((1S,2S)-2-vinyl-cyclopropyl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxy]-dimethyl-silane | 190005-26-6

• 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: tert-Butyl-[(3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((1S,2S)-2-vinyl-cyclopropyl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxy]-dimethyl-silane
• 英文别名: tert-butyl-[[(3S,8S,9S,10R,13R,14S,17R)-17-[(1S,2S)-2-ethenylcyclopropyl]-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl]oxy]-dimethylsilane
• CAS: 190005-26-6
• 化学式: C₃₀H₅₀OSi
• 分子量: 454.812
• InChiKey: KZQQODYHKPKCGY-RQXKJPNNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.78
• 重原子数：
  32.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  丙酮 、 tert-Butyl-[(3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((1S,2S)-2-vinyl-cyclopropyl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxy]-dimethyl-silane 在 正丁基锂 、 zirconocene dichloride 、 氢氟酸 作用下， 生成 (3S,8S,9S,10R,13R,14S,17R)-17-[(E,2S)-6-hydroxy-6-methylhept-3-en-2-yl]-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-ol
  参考文献：
  名称：

  Complexation of Vinylcyclopropanes with Zirconocene−1-butene Complex:  Application to the Stereocontrolled Synthesis of Steroidal Side Chains

  摘要：

  Reactions of vinylcyclopropane derivatives with a zirconocene-1-butene complex (''Cp2Zr'') caused regioselective cleavage of the cyclopropyl bond to give eta(3) pi-allylic and/or eta(1) sigma-allylic complexes. The regioselectivity of the bond cleavage and the formation of a eta(3) pi-allylic or eta(1) sigma-allylic complex depend on the bulkiness of the substituents on the cyclopropyl group and the presence of leaving functionality. A catalytic use of ''Cp2Zr'' in the presence of excess Grignard reagent also caused a ring opening of the vinylcyclopropane derivatives with the same sense of regiochemical selectivity. The reaction of the thermally equilibrated ''Cp2Zr''-propenylcyclopropane complex with acetone indicated the possibility for the synthesis of the steroidal side chain in either natural or unnatural forms. The synthetic utility of the present ''Cp2Zr''-vinylcyclopropane chemistry was ascertained by the stereocontrolled preparation of the C-20, C-24 dimethylated steroidal side chain which is identical to the active metabolite of vitamin D-2.

  DOI：

  10.1021/jo962064r
• 作为产物：
  描述：

  {2-[(3S,8S,9S,10R,13S,14S,17R)-3-(tert-Butyl-dimethyl-silanyloxy)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl]-cyclopropyl}-methanol 在 正丁基锂 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 15.0h， 生成 tert-Butyl-[(3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((1S,2S)-2-vinyl-cyclopropyl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxy]-dimethyl-silane
  参考文献：
  名称：

  Complexation of Vinylcyclopropanes with Zirconocene−1-butene Complex:  Application to the Stereocontrolled Synthesis of Steroidal Side Chains

  摘要：

  Reactions of vinylcyclopropane derivatives with a zirconocene-1-butene complex (''Cp2Zr'') caused regioselective cleavage of the cyclopropyl bond to give eta(3) pi-allylic and/or eta(1) sigma-allylic complexes. The regioselectivity of the bond cleavage and the formation of a eta(3) pi-allylic or eta(1) sigma-allylic complex depend on the bulkiness of the substituents on the cyclopropyl group and the presence of leaving functionality. A catalytic use of ''Cp2Zr'' in the presence of excess Grignard reagent also caused a ring opening of the vinylcyclopropane derivatives with the same sense of regiochemical selectivity. The reaction of the thermally equilibrated ''Cp2Zr''-propenylcyclopropane complex with acetone indicated the possibility for the synthesis of the steroidal side chain in either natural or unnatural forms. The synthetic utility of the present ''Cp2Zr''-vinylcyclopropane chemistry was ascertained by the stereocontrolled preparation of the C-20, C-24 dimethylated steroidal side chain which is identical to the active metabolite of vitamin D-2.

  DOI：

  10.1021/jo962064r