(1'S,2'S,5'S)-ethyl 2-[(2'-tert-butyldimethylsiloxypinylidene)amino]acetate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (1'S,2'S,5'S)-ethyl 2-[(2'-tert-butyldimethylsiloxypinylidene)amino]acetate
• 英文别名: ethyl 2-[[(1S,2S,5S)-2-[tert-butyl(dimethyl)silyl]oxy-2,6,6-trimethyl-3-bicyclo[3.1.1]heptanylidene]amino]acetate
• 化学式: C₂₀H₃₇NO₃Si
• 分子量: 367.604
• InChiKey: AKDGYANOASVOAZ-AVYPCKFXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.84
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  二溴二氟甲烷 、 (1'S,2'S,5'S)-ethyl 2-[(2'-tert-butyldimethylsiloxypinylidene)amino]acetate 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 4.5h， 以0.297 g的产率得到(1'S,2'S,5'S,2S)-ethyl 2-[(2'-tert-butyldimethylsiloxypinylidene)amino]-3-bromo-3,3-difluoropropanoate
  参考文献：
  名称：

  Efficient synthesis of an optically pure β-bromo-β,β-difluoroalanine derivative, a general precursor for β,β-difluoroamino acids

  摘要：

  A highly efficient enantioselective preparation of a beta -bromo-beta,beta -difluoroalanine derivative, a promising general precursor for optically active beta,beta -difluoroamino acids, is described. Alkylation of the hydroxypinanone glycinate Schiff base 2a with CF2Br2 resulted in the production of undesired dehydrobrominated product 4a promoted by the lithium alkoxide moiety on the hydroxypinanone chiral auxiliary. Dehydrobromination was prevented by protection of the hydroxyl group on the chiral auxiliary. Utilization of TMSOTf resulted in production of (S,S,S,S)-3b as the sole diastereomer without dehydrobromination. Further transformations of (S,S,S,S)-3b to other optically active beta,beta -difluoroamino acids were demonstrated. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00237-3
• 作为产物：
  描述：

  叔丁基二甲硅基三氟甲磺酸酯 、 (1S,2S,5S)-乙基[(2-羟基蒎烷-3-基烯)氨基]乙酸酯 在 2,6-二甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以97%的产率得到(1'S,2'S,5'S)-ethyl 2-[(2'-tert-butyldimethylsiloxypinylidene)amino]acetate
  参考文献：
  名称：

  Efficient synthesis of an optically pure β-bromo-β,β-difluoroalanine derivative, a general precursor for β,β-difluoroamino acids

  摘要：

  A highly efficient enantioselective preparation of a beta -bromo-beta,beta -difluoroalanine derivative, a promising general precursor for optically active beta,beta -difluoroamino acids, is described. Alkylation of the hydroxypinanone glycinate Schiff base 2a with CF2Br2 resulted in the production of undesired dehydrobrominated product 4a promoted by the lithium alkoxide moiety on the hydroxypinanone chiral auxiliary. Dehydrobromination was prevented by protection of the hydroxyl group on the chiral auxiliary. Utilization of TMSOTf resulted in production of (S,S,S,S)-3b as the sole diastereomer without dehydrobromination. Further transformations of (S,S,S,S)-3b to other optically active beta,beta -difluoroamino acids were demonstrated. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00237-3

文献信息

• Efficient synthesis of an optically pure β-bromo-β,β-difluoroalanine derivative, a general precursor for β,β-difluoroamino acids
  作者：Toshimasa Katagiri、Michiharu Handa、Yasuhisa Matsukawa、J.S. Dileep Kumar、Kenji Uneyama

  DOI：10.1016/s0957-4166(01)00237-3

  日期：2001.6

  A highly efficient enantioselective preparation of a beta -bromo-beta,beta -difluoroalanine derivative, a promising general precursor for optically active beta,beta -difluoroamino acids, is described. Alkylation of the hydroxypinanone glycinate Schiff base 2a with CF2Br2 resulted in the production of undesired dehydrobrominated product 4a promoted by the lithium alkoxide moiety on the hydroxypinanone chiral auxiliary. Dehydrobromination was prevented by protection of the hydroxyl group on the chiral auxiliary. Utilization of TMSOTf resulted in production of (S,S,S,S)-3b as the sole diastereomer without dehydrobromination. Further transformations of (S,S,S,S)-3b to other optically active beta,beta -difluoroamino acids were demonstrated. (C) 2001 Elsevier Science Ltd. All rights reserved.