(1S,2R,5S,6R,8R,9S,11R)-11-(2-Benzenesulfonyl-ethyl)-5-(tert-butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-6,10,10-trimethyl-12-oxo-13-oxa-tricyclo[6.4.1.0^1,6]tridecane-9-carboxylic acid methyl ester | 166533-88-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1S,2R,5S,6R,8R,9S,11R)-11-(2-Benzenesulfonyl-ethyl)-5-(tert-butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-6,10,10-trimethyl-12-oxo-13-oxa-tricyclo[6.4.1.0^1,6]tridecane-9-carboxylic acid methyl ester
• 英文别名: methyl (1S,2R,5S,6R,8R,9S,11R)-11-[2-(benzenesulfonyl)ethyl]-5-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6,10,10-trimethyl-12-oxo-13-oxatricyclo[6.4.1.01,6]tridecane-9-carboxylate
• CAS: 166533-88-6
• 化学式: C₃₈H₆₄O₈SSi₂
• 分子量: 737.158
• InChiKey: NOROJQZTXSJBCO-CLUPMQJSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.22
• 重原子数：
  49
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (1S,2R,5S,6R,8R,9S,11R)-11-(2-Benzenesulfonyl-ethyl)-5-(tert-butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-6,10,10-trimethyl-12-oxo-13-oxa-tricyclo[6.4.1.0^1,6]tridecane-9-carboxylic acid methyl ester 在 potassium tert-butylate 、 氧气 、 叔丁醇 、 亚磷酸三乙酯 作用下， 生成 (1S,2R,5S,6R,8R,9S,11S)-11-(2-Benzenesulfonyl-ethyl)-5-(tert-butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-11-hydroxy-6,10,10-trimethyl-12-oxo-13-oxa-tricyclo[6.4.1.0^1,6]tridecane-9-carboxylic acid methyl ester
  参考文献：
  名称：

  New Strategy for the Synthesis of the Taxane Diterpenes: Formation of the A-Ring and Introduction of the C-1 Hydroxyl Group

  摘要：

  DOI：

  10.1016/00404-0399(50)1084u-
• 作为产物：
  描述：

  (1S,2R,5S,6R,8R,11R)-11-(2-Benzenesulfonyl-ethyl)-5-(tert-butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-6,10,10-trimethyl-12-oxo-13-oxa-tricyclo[6.4.1.0^1,6]tridecane-9-carbaldehyde 在 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 potassium carbonate 作用下， 以 丙酮 、 叔丁醇 为溶剂， 反应 2.0h， 生成 (1S,2R,5S,6R,8R,9S,11R)-11-(2-Benzenesulfonyl-ethyl)-5-(tert-butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-6,10,10-trimethyl-12-oxo-13-oxa-tricyclo[6.4.1.0^1,6]tridecane-9-carboxylic acid methyl ester
  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

• Taxane diterpenes 4: Autoxidation, epimerization and isomerization for the introduction of functionality into the taxane ABC ring system
  作者：Philip Magnus、Feroze Ujjainwalla、Nicholas Westwood、Vince Lynch

  DOI：10.1016/s0040-4020(98)00056-8

  日期：1998.3

  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.
• New Strategy for the Synthesis of the Taxane Diterpenes: Formation of the A-Ring and Introduction of the C-1 Hydroxyl Group
  作者：P Magnus

  DOI：10.1016/00404-0399(50)1084u-

  日期：1995.7.24