tert-butyl (Z,4R)-3-amino-4-trimethylsilyloxyhept-2-enoate | 206352-51-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: tert-butyl (Z,4R)-3-amino-4-trimethylsilyloxyhept-2-enoate
• CAS: 206352-51-4
• 化学式: C₁₄H₂₉NO₃Si
• 分子量: 287.475
• InChiKey: GBCRKBSPWIJFAI-NLYDNYMLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.19
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  61.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-butyl (Z,4R)-3-amino-4-trimethylsilyloxyhept-2-enoate 在 盐酸 、 sodium cyanoborohydride 作用下， 以 甲醇 为溶剂， 反应 4.0h， 以71%的产率得到tert-butyl (4R)-3-amino-4-hydroxyheptanoate
  参考文献：
  名称：

  Application of the Blaise reaction: stereoselective synthesis of (4R)-tert-butyl 3-amino-4-trimethylsilyloxy-2-alkenoates from (R)-cyanohydrins

  摘要：

  O-Trimethylsilyl protected (R)-cyanohydrins 3 react with Reformatsky reagents from tert-butyl 2-bromoesters 4 and zinc dust (Blaise reaction) to give the corresponding addition products in high yields. Workup with an aqueous solution of NH4Cl at low temperature gives (4R)-tert-butyl 3-amino-4-trimethylsilyloxy-2-alkenoates (R)-5 without racemization. Hydrogenation of the alkenoates 5 to the corresponding tert-butyl beta-amino-gamma-hydroxyalkanoates 6, resulting in a mixture of two diastereoisomers, was only possible under special hydrogenation conditions. With HCl in dichloromethane compounds 6 cyclize to the corresponding beta-amino-gamma-hydroxybutyrolactones 8. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(98)00039-1
• 作为产物：
  描述：

  溴乙酸叔丁酯 、 (R)-2-(Trimethylsiloxy)pentannitril 在 锌 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以83%的产率得到tert-butyl (Z,4R)-3-amino-4-trimethylsilyloxyhept-2-enoate
  参考文献：
  名称：

  Application of the Blaise reaction: stereoselective synthesis of (4R)-tert-butyl 3-amino-4-trimethylsilyloxy-2-alkenoates from (R)-cyanohydrins

  摘要：

  O-Trimethylsilyl protected (R)-cyanohydrins 3 react with Reformatsky reagents from tert-butyl 2-bromoesters 4 and zinc dust (Blaise reaction) to give the corresponding addition products in high yields. Workup with an aqueous solution of NH4Cl at low temperature gives (4R)-tert-butyl 3-amino-4-trimethylsilyloxy-2-alkenoates (R)-5 without racemization. Hydrogenation of the alkenoates 5 to the corresponding tert-butyl beta-amino-gamma-hydroxyalkanoates 6, resulting in a mixture of two diastereoisomers, was only possible under special hydrogenation conditions. With HCl in dichloromethane compounds 6 cyclize to the corresponding beta-amino-gamma-hydroxybutyrolactones 8. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(98)00039-1

文献信息

• Stereoselective synthesis of biologically active tetronic acids
  作者：Franz Effenberger、Jana Syed

  DOI：10.1016/s0957-4166(98)00040-8

  日期：1998.3

  (4R)-3-Amino-4-trimethylsilyloxy-2-alkenoates (R)-3, obtained from O-trimethylsilyl protected optically active cyanohydrins (R)-1 via the Blaise reaction, are hydrolyzed under mildly acidic conditions to give optically active tetronic acids (R)-4 without racemization. From the follow-up reactions of (R)-4 investigated, only methylation with diazomethane afforded the biologically active tetronic acid derivative (R)-5a without racemization whereas acylation and reductive alkylation, respectively, resulted in partial racemization or failed on the whole. (C) 1998 Elsevier Science Ltd. All rights reserved.

  由O-三甲基硅基保护的光学活性腈酮（R)-1通过Blaise反应得到的(4R)-3-氨基-4-三甲基硅基氧基-2-烯酸酯（R)-3，在温和酸性条件下水解生成无外消旋化的光学活性四氢嘧啶酸（R)-4。对（R)-4的后续反应研究表明，仅甲亚胺的甲基化反应可以得到无外消旋化的生物活性四氢嘧啶酸衍生物（R)-5a，而酰化和还原烷基化分别导致部分外消旋化或完全失败。©1998 Elsevier Science Ltd. 保留所有权利。
• Application of the Blaise reaction: stereoselective synthesis of (4R)-tert-butyl 3-amino-4-trimethylsilyloxy-2-alkenoates from (R)-cyanohydrins
  作者：Jana Syed、Siegfried Förster、Franz Effenberger

  DOI：10.1016/s0957-4166(98)00039-1

  日期：1998.3

  O-Trimethylsilyl protected (R)-cyanohydrins 3 react with Reformatsky reagents from tert-butyl 2-bromoesters 4 and zinc dust (Blaise reaction) to give the corresponding addition products in high yields. Workup with an aqueous solution of NH4Cl at low temperature gives (4R)-tert-butyl 3-amino-4-trimethylsilyloxy-2-alkenoates (R)-5 without racemization. Hydrogenation of the alkenoates 5 to the corresponding tert-butyl beta-amino-gamma-hydroxyalkanoates 6, resulting in a mixture of two diastereoisomers, was only possible under special hydrogenation conditions. With HCl in dichloromethane compounds 6 cyclize to the corresponding beta-amino-gamma-hydroxybutyrolactones 8. (C) 1998 Elsevier Science Ltd. All rights reserved.