4β,11β-dihydro-4-carboxy-7β-(tert-butyldimethylsilyl)oxy-3α,10α-oxido-taxane-12-ene-2-one | 182236-66-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: 4β,11β-dihydro-4-carboxy-7β-(tert-butyldimethylsilyl)oxy-3α,10α-oxido-taxane-12-ene-2-one
• 英文别名: (1S,3R,7S,8R,10R,11S,14S)-11-[tert-butyl(dimethyl)silyl]oxy-6,10,16,16-tetramethyl-2-oxo-15-oxatetracyclo[6.6.1.13,7.01,10]hexadec-5-ene-14-carboxylic acid
• CAS: 182236-66-4
• 化学式: C₂₆H₄₂O₅Si
• 分子量: 462.702
• InChiKey: VUKNZINHGSLBTK-JTLIVKAVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4β,11β-dihydro-4-carboxy-7β-(tert-butyldimethylsilyl)oxy-3α,10α-oxido-taxane-12-ene-2-one 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 以63%的产率得到4β,11β-dihydro-7β-(tert-butyldimethylsilyl)oxy-2α,20α-oxido-20-oxo-taxane-3,12-diene-10-one
  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：

  methyl 1α-(2'-phenylsulfonylethyl)-2β-methoxy-7β-(tert-butyldimethylsilyl)oxy-3α,10α-oxido-8β,12,12-trimethylbicyclo[6.4.0^3,8]dodec-11α-oate 在 sodium chlorite 、 sodium dihydrogenphosphate 、 copper(l) iodide 、 2-甲基-2-丁烯 、 氨 、 sodium hexamethyldisilazane 、 sodium 、 戴斯-马丁氧化剂 、 溶剂黄146 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 72.75h， 生成 4β,11β-dihydro-4-carboxy-7β-(tert-butyldimethylsilyl)oxy-3α,10α-oxido-taxane-12-ene-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