(2aR,4S,4aS,9S,11S,12S,12aR,12bS)-11,12-dihydroxy-4a,8,13,13-tetramethyl-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]oxet-12b(2aH)-yl acetate | 155370-84-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (2aR,4S,4aS,9S,11S,12S,12aR,12bS)-11,12-dihydroxy-4a,8,13,13-tetramethyl-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]oxet-12b(2aH)-yl acetate
• CAS: 155370-84-6
• 化学式: C₃₄H₆₀O₈Si₂
• 分子量: 653.017
• InChiKey: NXBFQFDYSMLCCD-XKDFRECOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.31
• 重原子数：
  44.0
• 可旋转键数：
  11.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  111.52
• 氢给体数：
  2.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  二硫化碳 、 (2aR,4S,4aS,9S,11S,12S,12aR,12bS)-11,12-dihydroxy-4a,8,13,13-tetramethyl-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]oxet-12b(2aH)-yl acetate 、 碘甲烷 在 sodium hydride 作用下， 生成 、 (3aS,5S,9aS,10S,11aR,13aS,13bR,13cS)-6,9a,14,14-tetramethyl-9-oxo-2-thioxo-5,10-bis((triethylsilyl)oxy)-4,5,8,9,9a,10,11,11a,13b,13c-decahydro-3a,7-methanooxeto[2'',3'':5',6']benzo[1',2':3,4]cyclodeca[1,2-d][1,3]dioxol-13a(13H)-yl acetate
  参考文献：
  名称：

  The Chemistry of Taxanes: Skeletal Rearrangements of Baccatin Derivatives via Radical Intermediates

  摘要：

  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.

  DOI：

  10.1021/jo00085a040
• 作为产物：
  描述：

  10-脱乙酰基巴卡丁 III 在 咪唑 、 正丁基锂 、 偶氮二异丁腈 、 三正丁基氢锡 、 红铝 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 3.84h， 生成 (2aR,4S,4aS,9S,11S,12S,12aR,12bS)-11,12-dihydroxy-4a,8,13,13-tetramethyl-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]oxet-12b(2aH)-yl acetate
  参考文献：
  名称：

  The Chemistry of Taxanes: Skeletal Rearrangements of Baccatin Derivatives via Radical Intermediates

  摘要：

  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.

  DOI：

  10.1021/jo00085a040