(1R,3S,7S,8S,10R,11S)-7-(tert-Butyl-dimethyl-silanyloxy)-10-hydroxy-4-hydroxymethyl-8,12,15,15-tetramethyl-tricyclo[9.3.1.0^3,8]pentadeca-4,12-dien-2-one | 182236-76-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R,3S,7S,8S,10R,11S)-7-(tert-Butyl-dimethyl-silanyloxy)-10-hydroxy-4-hydroxymethyl-8,12,15,15-tetramethyl-tricyclo[9.3.1.0^3,8]pentadeca-4,12-dien-2-one
• CAS: 182236-76-6
• 化学式: C₂₆H₄₄O₄Si
• 分子量: 448.718
• InChiKey: ARSMRRZEHJMHCQ-APWIYRHCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.26
• 重原子数：
  31.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  66.76
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (1R,3S,7S,8S,10R,11S)-7-(tert-Butyl-dimethyl-silanyloxy)-10-hydroxy-4-hydroxymethyl-8,12,15,15-tetramethyl-tricyclo[9.3.1.0^3,8]pentadeca-4,12-dien-2-one 在 4-二甲氨基吡啶 、 potassium tert-butylate 、 氧气 、 戴斯-马丁氧化剂 、 三乙胺 、 亚磷酸三乙酯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.75h， 生成 (1S,3S,7S,8S,11S)-7-(tert-Butyl-dimethyl-silanyloxy)-4-(tert-butyl-dimethyl-silanyloxymethyl)-1-hydroxy-8,12,15,15-tetramethyl-tricyclo[9.3.1.0^3,8]pentadeca-4,12-diene-2,10-dione
  参考文献：
  名称：

  Taxane diterpenes 4: Autoxidation, epimerization and isomerization for the introduction of functionality into the taxane ABC ring system

  摘要：

  The bicyclo[5.4.0]undecenone 4 was converted through a four step sequence involving activation, gem-methylcyclopropanation and reductive cleavage into 18 alpha/beta, containing the B/C rings of the taxanes. The A-ring has been attached to the B/C ring system by cyclization of the sulfone-ester 23 alpha to give 24. The A-ring was modified to give 29, which underwent beta-elimination of the 3,10-oxido bridge via a dianion, followed by transannular hydride shift to give the butenolide 30 and 32. Autoxidation of 30 gave 33 which was further elaborated into the trans-fused B/C adduct 35. The isomeric 3,10-diones trans-39 and cis-45 undergo autoxidation using t-BuOK/THF/O-2/P(OEt)(3) to give 2 and 46 respectively without B/C cis/trans isomerization. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00056-8
• 作为产物：
  描述：

  (1R,3R,7S,8S,10R,11S)-7-(tert-Butyl-dimethyl-silanyloxy)-10-hydroxy-8,12,15,15-tetramethyl-2-oxo-tricyclo[9.3.1.0^3,8]pentadeca-4,12-diene-4-carboxylic acid 在 硼烷四氢呋喃络合物 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以75%的产率得到(1R,3S,7S,8S,10R,11S)-7-(tert-Butyl-dimethyl-silanyloxy)-10-hydroxy-4-hydroxymethyl-8,12,15,15-tetramethyl-tricyclo[9.3.1.0^3,8]pentadeca-4,12-dien-2-one
  参考文献：
  名称：

  Taxane diterpenes 4: Autoxidation, epimerization and isomerization for the introduction of functionality into the taxane ABC ring system

  摘要：

  The bicyclo[5.4.0]undecenone 4 was converted through a four step sequence involving activation, gem-methylcyclopropanation and reductive cleavage into 18 alpha/beta, containing the B/C rings of the taxanes. The A-ring has been attached to the B/C ring system by cyclization of the sulfone-ester 23 alpha to give 24. The A-ring was modified to give 29, which underwent beta-elimination of the 3,10-oxido bridge via a dianion, followed by transannular hydride shift to give the butenolide 30 and 32. Autoxidation of 30 gave 33 which was further elaborated into the trans-fused B/C adduct 35. The isomeric 3,10-diones trans-39 and cis-45 undergo autoxidation using t-BuOK/THF/O-2/P(OEt)(3) to give 2 and 46 respectively without B/C cis/trans isomerization. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00056-8

文献信息

• Isomerization, autoxidation and epimerization for the introduction of C-1 to C-5 functionality into the taxane ABC ring system
  作者：Philip Magnus、Feroze Ujjainwalla、Nicholas Westwood、Vince Lynch

  DOI：10.1016/s0040-4039(96)01495-5

  日期：1996.9

  Treatment of 2-ketotax-3-enes with r-BuOK/t-BuOH/THF/65 degrees C results in isomerization of the double bond into the 4,5-position and a trans-B/C ring fusion. Subsequent exposure to t-BuOK/THF/O-2/P(OEt)(3) introduces the C-1-hydroxyl group. Copyright (C) 1996 Elsevier Science Ltd