4β,11β-dihydro-7β-(tert-butyldimethylsilyl)oxy-3α,10α-oxido-2α,20α-oxido-2β-methoxy-12-nortaxane-12-one | 166533-91-1

• 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-7β-(tert-butyldimethylsilyl)oxy-3α,10α-oxido-2α,20α-oxido-2β-methoxy-12-nortaxane-12-one
• 英文别名: (1S,2R,4S,5R,6S,9R,12R,13R)-6-[tert-butyl(dimethyl)silyl]oxy-12-methoxy-5,17,17-trimethyl-3,11-dioxapentacyclo[11.3.1.12,5.04,9.04,12]octadecan-16-one
• CAS: 166533-91-1
• 化学式: C₂₆H₄₄O₅Si
• 分子量: 464.718
• InChiKey: PIGZEPDFCMTWQT-FUKWOJNNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.33
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4β,11β-dihydro-7β-(tert-butyldimethylsilyl)oxy-3α,10α-oxido-2α,20α-oxido-2β-methoxy-12-nortaxane-12-one 在 sodium chlorite 、 sodium dihydrogenphosphate 、 copper(l) iodide 、 2-甲基-2-丁烯 、 sodium hexamethyldisilazane 、 戴斯-马丁氧化剂 、 溶剂黄146 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 71.25h， 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
• 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 氨 、 sodium 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 生成 4β,11β-dihydro-7β-(tert-butyldimethylsilyl)oxy-3α,10α-oxido-2α,20α-oxido-2β-methoxy-12-nortaxane-12-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

• 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
• 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.