(2aR,4S,4aS,6R,9S,11S,12S,12aR,12bS)-11-hydroxy-4a,8,13,13-tetramethyl-12-(((methylthio)carbonothioyl)oxy)-5-oxo-4,9-bis((triethylsilyl)oxy)-3,4,4a,5,6,9,10,11,12,12a-decahydro-1H-7,11-methanocyclodeca[3,4]benzo[1,2-b]oxete-6,12b(2aH)-diyl diacetate | 150542-02-2

• 英文名称: (2aR,4S,4aS,6R,9S,11S,12S,12aR,12bS)-11-hydroxy-4a,8,13,13-tetramethyl-12-(((methylthio)carbonothioyl)oxy)-5-oxo-4,9-bis((triethylsilyl)oxy)-3,4,4a,5,6,9,10,11,12,12a-decahydro-1H-7,11-methanocyclodeca[3,4]benzo[1,2-b]oxete-6,12b(2aH)-diyl diacetate
• CAS: 150542-02-2
• 化学式: C₃₈H₆₄O₁₀S₂Si₂
• 分子量: 801.223
• InChiKey: SWQRNKIPFIHODN-AHQDNHDTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.52
• 重原子数：
  52.0
• 可旋转键数：
  13.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  126.82
• 氢给体数：
  1.0
• 氢受体数：
  12.0

反应信息

• 作为反应物：
  描述：

  (2aR,4S,4aS,6R,9S,11S,12S,12aR,12bS)-11-hydroxy-4a,8,13,13-tetramethyl-12-(((methylthio)carbonothioyl)oxy)-5-oxo-4,9-bis((triethylsilyl)oxy)-3,4,4a,5,6,9,10,11,12,12a-decahydro-1H-7,11-methanocyclodeca[3,4]benzo[1,2-b]oxete-6,12b(2aH)-diyl diacetate 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 以89%的产率得到
  参考文献：
  名称：

  紫杉醇构效关系：2-脱氧紫杉醇的合成及生物学评价

  摘要：

  从浆果赤霉素III中分九步制备2-脱氧紫杉醇2。合成的关键步骤是C-2处的Barton型脱氧。发现该化合物相对于紫杉醇具有大大降低的抗肿瘤活性。

  DOI：

  10.1016/s0040-4039(00)73661-6
• 作为产物：
  描述：

  巴卡丁 III 在 咪唑 、 sodium methylate 、 sodium hydride 、 碘甲烷 作用下， 以 甲醇 为溶剂， 生成 (2aR,4S,4aS,6R,9S,11S,12S,12aR,12bS)-11-hydroxy-4a,8,13,13-tetramethyl-12-(((methylthio)carbonothioyl)oxy)-5-oxo-4,9-bis((triethylsilyl)oxy)-3,4,4a,5,6,9,10,11,12,12a-decahydro-1H-7,11-methanocyclodeca[3,4]benzo[1,2-b]oxete-6,12b(2aH)-diyl diacetate
  参考文献：
  名称：

  紫杉醇构效关系：2-脱氧紫杉醇的合成及生物学评价

  摘要：

  从浆果赤霉素III中分九步制备2-脱氧紫杉醇2。合成的关键步骤是C-2处的Barton型脱氧。发现该化合物相对于紫杉醇具有大大降低的抗肿瘤活性。

  DOI：

  10.1016/s0040-4039(00)73661-6

文献信息

• The Chemistry of Taxanes: Skeletal Rearrangements of Baccatin Derivatives via Radical Intermediates
  作者：Shu-Hui Chen、Stella Huang、Qi Gao、Jerzy Golik、Vittorio Farina

  DOI：10.1021/jo00085a040

  日期：1994.3

  In the course of a synthetic program aimed at systematic defunctionalization of the taxol core for structure activity studies, a number of radical-based deoxygenation reactions were carried out on baccatin III derivatives. In this connection, we have discovered that formation of radicals at positions C-1, C-2, and C-7 in the taxane core of baccatin III results in a number of skeletal rearrangement cascades. Furthermore, the exact composition of the product mixture depends on the specific tin (or silicon) hydride used for the reduction. In the case of C-2- and C-7-derived radicals, direct quenching with tin hydrides without rearrangement was possible under some conditions. However, we were unable to find conditions to quench the C-1 radical, since rearrangement pathways always predominate in this case.