(5S)-3-isopropyl-5-trimethylsilylimidazolidine-1-carboxylic acid tert-butyl ester | 381210-82-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (5S)-3-isopropyl-5-trimethylsilylimidazolidine-1-carboxylic acid tert-butyl ester
• 英文别名: tert-butyl (5S)-3-propan-2-yl-5-trimethylsilylimidazolidine-1-carboxylate
• CAS: 381210-82-8
• 化学式: C₁₄H₃₀N₂O₂Si
• 分子量: 286.49
• InChiKey: BVUPGBVIHSENPJ-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.15
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  32.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (5S)-3-isopropyl-5-trimethylsilylimidazolidine-1-carboxylic acid tert-butyl ester 在 丙二酸 作用下， 以 吡啶 、 乙醇 为溶剂， 以84%的产率得到(1S)-(2-isopropylamino-1-trimethylsilylethyl)carbamic acid tert-butyl ester
  参考文献：
  名称：

  Synthesis of Chiral 1,2-Diamines by Asymmetric Lithiation−Substitution

  摘要：

  [GRAPHICS]The imidazolidine (tetrahydrolmidazole) 2, prepared in one step from N-iso-propylethylenediamine, was subjected to asymmetric lithiation and substitution using sec-butyllithium, (-)-sparteine and a range of electrophiles. Substituted imidazolidines were formed with high optical purity and could be hydrolyzed under acidic conditions to chiral, substituted ethylenediamines. Kinetic data indicate that the conformation of the carbonyl group is crucial to the extent of deprotonation, and this has implications for the lithiation of unsymmetrical carbamates and carboxylic amides.

  DOI：

  10.1021/ol016818m
• 作为产物：
  描述：

  N-异丙基乙二胺 在 仲丁基锂 、 magnesium sulfate 、 potassium carbonate 、 鹰爪豆碱 作用下， 以 乙醚 、 氯仿 、 环己烷 为溶剂， 反应 42.0h， 生成 (5S)-3-isopropyl-5-trimethylsilylimidazolidine-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Preparation of diamines by lithiation–substitution of imidazolidines and pyrimidines

  摘要：

  通过未取代的二胺合成手性1,2-二胺和1,3-二胺的方法是，先使二胺与N-叔丁氧羰基（Boc）取代的咪唑啉（四氢咪唑）或嘧啶（六氢-1,3-二嗪）反应，再用仲丁基锂处理，使α位上的氢原子去质子化并与N-Boc基团反应，接着加入亲电试剂得到取代产物，后者在酸性条件下水解后可得到取代的1,2-或1,3-二胺。使用手性配体（-）-鹰爪豆碱能促进咪唑啉底物的非对称去质子化，水解后得到旋光纯度较高的1,2-二胺。

  DOI：

  10.1039/b301502e

文献信息

• Preparation of diamines by lithiation–substitution of imidazolidines and pyrimidines
  作者：Neil J. Ashweek、Iain Coldham、Thomas F. N. Haxell、Steven Howard

  DOI：10.1039/b301502e

  日期：2003.4.23

  The synthesis of chiral 1,2-diamines and 1,3-diamines was achieved from the unsubstituted diamines by way of N-tert-butoxycarbonyl (Boc) substituted imidazolidines (tetrahydroimidazoles) and pyrimidines (hexahydro-1,3-diazines), which were treated with sec-butyllithium to effect deprotonation α- to the N-Boc group, followed by addition of an electrophile to give substituted products that could be hydrolysed under acidic conditions to give the substituted 1,2- or 1,3-diamines. Use of the chiral ligand (−)-sparteine promoted asymmetric deprotonation of the imidazolidine substrates to give, after hydrolysis, enantiomerically enriched 1,2-diamines.

  通过未取代的二胺合成手性1,2-二胺和1,3-二胺的方法是，先使二胺与N-叔丁氧羰基（Boc）取代的咪唑啉（四氢咪唑）或嘧啶（六氢-1,3-二嗪）反应，再用仲丁基锂处理，使α位上的氢原子去质子化并与N-Boc基团反应，接着加入亲电试剂得到取代产物，后者在酸性条件下水解后可得到取代的1,2-或1,3-二胺。使用手性配体（-）-鹰爪豆碱能促进咪唑啉底物的非对称去质子化，水解后得到旋光纯度较高的1,2-二胺。
• Synthesis of Chiral 1,2-Diamines by Asymmetric Lithiation−Substitution
  作者：Iain Coldham、Royston C. B. Copley、Thomas F. N. Haxell、Steven Howard

  DOI：10.1021/ol016818m

  日期：2001.11.1

  [GRAPHICS]The imidazolidine (tetrahydrolmidazole) 2, prepared in one step from N-iso-propylethylenediamine, was subjected to asymmetric lithiation and substitution using sec-butyllithium, (-)-sparteine and a range of electrophiles. Substituted imidazolidines were formed with high optical purity and could be hydrolyzed under acidic conditions to chiral, substituted ethylenediamines. Kinetic data indicate that the conformation of the carbonyl group is crucial to the extent of deprotonation, and this has implications for the lithiation of unsymmetrical carbamates and carboxylic amides.