S-tert-butyl 2-[tert-butyl(dimethyl)silyl]oxyethanethioate | 186596-34-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: S-tert-butyl 2-[tert-butyl(dimethyl)silyl]oxyethanethioate
• CAS: 186596-34-9
• 化学式: C₁₂H₂₆O₂SSi
• 分子量: 262.489
• InChiKey: WMNWSAIXRPILFB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.07
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  S-tert-butyl 2-[tert-butyl(dimethyl)silyl]oxyethanethioate 在 4-甲基苯磺酸吡啶 作用下， 以 甲苯 为溶剂， 反应 4.0h， 生成 tert-butyl (4S,5R)-5-tert-butylsulfanylcarbonyl-2,2-dimethyl-4-phenyl-1,3-oxazolidine-3-carboxylate
  参考文献：
  名称：

  Taxol Semisynthesis:  A Highly Enantio- and Diastereoselective Synthesis of the Side Chain and a New Method for Ester Formation at C-13 Using Thioesters

  摘要：

  A very simple, new, and straightforward approach to the Paclitaxel (Taxol) and Docetaxel (Taxotere) side chains has been developed using the imine addition reaction of thioester-derived boron enolates bearing chiral ligands. The addition reaction was studied extensively, using a combination of different thioesters (ROCH2COSPh, ROCH(2)60St-Bu), oxygen protecting groups (R = Bn, TBDMS, COPh, EE, TMS), chiral boron ligands [derived from both (-) and (+)-menthone], imines (PhCH=NSiMe3, PhCH=NCOPh), and in the presence or in the absence of additional Lewis acids (BF3-OEt2, Et2AlCl, TiCl4). The side chain was assembled in a few steps with the correct relative (syn) and absolute stereochemistry (2R,3S). The stereochemical outcome of the boron-mediated reaction was rationalized using chair vs boat transition state structures. A new direct route for attachment of the side chains to the baccatin nucleus using thioester chemistry has also been developed. By treatment of a mixture of a thioester (8, 12, or 17) and protected baccatin III (2b, 2c) with LHMDS, the 13-O acylated compounds were obtained in high yield (up to 90%). Hydrolysis of 18b gave Paclitaxel (1a) in 80% yield.

  DOI：

  10.1021/jo9703212
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 咪唑 、 三甲基铝 作用下， 以 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 92.0h， 生成 S-tert-butyl 2-[tert-butyl(dimethyl)silyl]oxyethanethioate
  参考文献：
  名称：

  Taxol Semisynthesis:  A Highly Enantio- and Diastereoselective Synthesis of the Side Chain and a New Method for Ester Formation at C-13 Using Thioesters

  摘要：

  A very simple, new, and straightforward approach to the Paclitaxel (Taxol) and Docetaxel (Taxotere) side chains has been developed using the imine addition reaction of thioester-derived boron enolates bearing chiral ligands. The addition reaction was studied extensively, using a combination of different thioesters (ROCH2COSPh, ROCH(2)60St-Bu), oxygen protecting groups (R = Bn, TBDMS, COPh, EE, TMS), chiral boron ligands [derived from both (-) and (+)-menthone], imines (PhCH=NSiMe3, PhCH=NCOPh), and in the presence or in the absence of additional Lewis acids (BF3-OEt2, Et2AlCl, TiCl4). The side chain was assembled in a few steps with the correct relative (syn) and absolute stereochemistry (2R,3S). The stereochemical outcome of the boron-mediated reaction was rationalized using chair vs boat transition state structures. A new direct route for attachment of the side chains to the baccatin nucleus using thioester chemistry has also been developed. By treatment of a mixture of a thioester (8, 12, or 17) and protected baccatin III (2b, 2c) with LHMDS, the 13-O acylated compounds were obtained in high yield (up to 90%). Hydrolysis of 18b gave Paclitaxel (1a) in 80% yield.

  DOI：

  10.1021/jo9703212