(1S,2R,5S,6R,8R)-5-(tert-Butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-6-methyl-12-oxa-tricyclo[6.3.1.0^1,6]dodec-9-en-11-one | 166533-71-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (1S,2R,5S,6R,8R)-5-(tert-Butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-6-methyl-12-oxa-tricyclo[6.3.1.0^1,6]dodec-9-en-11-one
• 英文别名: (1S,2R,5S,6R,8R)-5-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-methyl-12-oxatricyclo[6.3.1.01,6]dodec-9-en-11-one
• CAS: 166533-71-7
• 化学式: C₂₅H₄₆O₄Si₂
• 分子量: 466.809
• InChiKey: HUXBHUHMMWMJQL-PPFZOCHVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.48
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,2R,5S,6R,8R)-5-(tert-Butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-6-methyl-12-oxa-tricyclo[6.3.1.0^1,6]dodec-9-en-11-one 在 溴 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以100%的产率得到(1S,2R,5S,6R,8R)-10-Bromo-5-(tert-butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-6-methyl-12-oxa-tricyclo[6.3.1.01,6]dodec-9-en-11-one
  参考文献：
  名称：

  合成紫杉烷二萜的新策略：通过[5 + 2]-吡啶鎓内鎓盐-烯烃环化形成紫杉醇的BC-环，环的扩展策略

  摘要：

  紫杉醇的BC环可以使用分子内的[5 + 2]-吡啶鎓内鎓盐-烯烃环化，然后通过宝石-甲基环丙烷化和内部环丙烷键的还原性裂解来合成。

  DOI：

  10.1016/0040-4039(95)01083-t
• 作为产物：
  描述：

  Acetic acid 6-[(1R,4S)-4-(tert-butyl-dimethyl-silanyloxy)-1-(tert-butyl-dimethyl-silanyloxymethyl)-5-methyl-hex-5-enyl]-5-oxo-5,6-dihydro-2H-pyran-2-yl ester 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲苯 为溶剂， 反应 18.0h， 以77%的产率得到(1S,2R,5S,6R,8R)-5-(tert-Butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-6-methyl-12-oxa-tricyclo[6.3.1.0^1,6]dodec-9-en-11-one
  参考文献：
  名称：

  紫杉烷二萜1.控制紫杉醇前体合成的分子内吡喃鎓内鎓盐-烯烃环化中的相对和绝对立体化学

  摘要：

  分子内吡咯鎓内鎓盐-烯烃环化提供对关键的C-19角甲基的绝对立体化学的控制，并导致包含紫杉烷类B / C环结构元素的双环[5.4.0 3,8 ]十一碳烯。

  DOI：

  10.1016/0040-4020(96)00867-8

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.