(2S,5S)-2,5-Dimethyl-pyrrolidine-1-carboxylic acid tert-butyl ester | 156038-84-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (2S,5S)-2,5-Dimethyl-pyrrolidine-1-carboxylic acid tert-butyl ester
• 英文别名: tert-Butyl (2S,5S)-2,5-dimethylpyrrolidine-1-carboxylate；tert-butyl (2S,5S)-2,5-dimethylpyrrolidine-1-carboxylate
• CAS: 156038-84-5
• 化学式: C₁₁H₂₁NO₂
• 分子量: 199.293
• InChiKey: FZSBLLYQAULJDU-IUCAKERBSA-N

物化性质

• 沸点：
  246.6±9.0 °C(Predicted)
• 密度：
  0.930 g/mL at 25 °C
• 闪点：
  86 °C

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,5S)-2,5-Dimethyl-pyrrolidine-1-carboxylic acid tert-butyl ester 在 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 (S,S)-2,5-dimethyl-N-(3,5-dinitrobenzoyl)pyrrolidine
  参考文献：
  名称：

  Complex Induced Proximity Effects: Enantioselective Syntheses Based on Asymmetric Deprotonations of N-Boc-pyrrolidines

  摘要：

  Lithiation of N-Boc-pyrrolidine (6) with sec-butyllithium (s-BuLi)/(-)-sparteine (14) effects an asymmetric deprotonation to give (S)-2-lithio-N-Boc-pyrrolidine ((S)-22),which reacts with electrophiles to provide the 2-substituted N-Boc-pyrrolidines 7-11 and 13 in enantiomeric excesses which generally are >90%. In the lithiation-silylation of 6 the chiral ligand 15 gives 7 with a lower enantiomeric excess and chiral ligands 16 and 17 give 7 with lower and opposite enantiomeric excesses than that obtained with 14. Diastereoselective amplification operates in a sequential lithiation-substitution sequence to provide the conversion of (S)-2-methyl-N-Boc-pyrrolidine ((S)-10) of 95% enantiomeric excess with s-BuLi/14 to (S,S)-2,5-dimethyl-N-Boc-pyrrolidine ((S,S)-19) with >99% enantiomeric excess. Synthetic preparations of a useful chiral ligand, (R)-alpha,alpha-diphenyl-2-pyrrolidine ((R)-20), and a useful chiral auxiliary, (S,S)2,5-dimethylpyrrolidine hydrochloride ((S,S)-21), are reported. Reactions of racemic and enantioenriched 2-lithio-N-Boc-pyrrolidine and investigation of sequential lithiations-deuterations of 6 establish the reaction pathway to be asymmetric deprotonation rather than asymmetric substitution. A rationalization for the enantioselective deprotonation is provided.

  DOI：

  10.1021/ja00087a008
• 作为产物：
  描述：

  硫酸二甲酯 、 (S)-1-叔丁氧羰基-2-甲基吡咯烷 在 仲丁基锂 、 鹰爪豆碱 作用下， 生成 (2S,5R)-2,5-Dimethyl-pyrrolidine-1-carboxylic acid tert-butyl ester 、 (2S,5S)-2,5-Dimethyl-pyrrolidine-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Complex Induced Proximity Effects: Enantioselective Syntheses Based on Asymmetric Deprotonations of N-Boc-pyrrolidines

  摘要：

  Lithiation of N-Boc-pyrrolidine (6) with sec-butyllithium (s-BuLi)/(-)-sparteine (14) effects an asymmetric deprotonation to give (S)-2-lithio-N-Boc-pyrrolidine ((S)-22),which reacts with electrophiles to provide the 2-substituted N-Boc-pyrrolidines 7-11 and 13 in enantiomeric excesses which generally are >90%. In the lithiation-silylation of 6 the chiral ligand 15 gives 7 with a lower enantiomeric excess and chiral ligands 16 and 17 give 7 with lower and opposite enantiomeric excesses than that obtained with 14. Diastereoselective amplification operates in a sequential lithiation-substitution sequence to provide the conversion of (S)-2-methyl-N-Boc-pyrrolidine ((S)-10) of 95% enantiomeric excess with s-BuLi/14 to (S,S)-2,5-dimethyl-N-Boc-pyrrolidine ((S,S)-19) with >99% enantiomeric excess. Synthetic preparations of a useful chiral ligand, (R)-alpha,alpha-diphenyl-2-pyrrolidine ((R)-20), and a useful chiral auxiliary, (S,S)2,5-dimethylpyrrolidine hydrochloride ((S,S)-21), are reported. Reactions of racemic and enantioenriched 2-lithio-N-Boc-pyrrolidine and investigation of sequential lithiations-deuterations of 6 establish the reaction pathway to be asymmetric deprotonation rather than asymmetric substitution. A rationalization for the enantioselective deprotonation is provided.

  DOI：

  10.1021/ja00087a008

文献信息

• Complex Induced Proximity Effects: Enantioselective Syntheses Based on Asymmetric Deprotonations of N-Boc-pyrrolidines
  作者：Peter Beak、Shawn T. Kerrick、Shengde Wu、Jingxi Chu

  DOI：10.1021/ja00087a008

  日期：1994.4

  Lithiation of N-Boc-pyrrolidine (6) with sec-butyllithium (s-BuLi)/(-)-sparteine (14) effects an asymmetric deprotonation to give (S)-2-lithio-N-Boc-pyrrolidine ((S)-22),which reacts with electrophiles to provide the 2-substituted N-Boc-pyrrolidines 7-11 and 13 in enantiomeric excesses which generally are >90%. In the lithiation-silylation of 6 the chiral ligand 15 gives 7 with a lower enantiomeric excess and chiral ligands 16 and 17 give 7 with lower and opposite enantiomeric excesses than that obtained with 14. Diastereoselective amplification operates in a sequential lithiation-substitution sequence to provide the conversion of (S)-2-methyl-N-Boc-pyrrolidine ((S)-10) of 95% enantiomeric excess with s-BuLi/14 to (S,S)-2,5-dimethyl-N-Boc-pyrrolidine ((S,S)-19) with >99% enantiomeric excess. Synthetic preparations of a useful chiral ligand, (R)-alpha,alpha-diphenyl-2-pyrrolidine ((R)-20), and a useful chiral auxiliary, (S,S)2,5-dimethylpyrrolidine hydrochloride ((S,S)-21), are reported. Reactions of racemic and enantioenriched 2-lithio-N-Boc-pyrrolidine and investigation of sequential lithiations-deuterations of 6 establish the reaction pathway to be asymmetric deprotonation rather than asymmetric substitution. A rationalization for the enantioselective deprotonation is provided.