(S)-4-Cyclohexyl-2-hydroxy-pyrrolidine-1-carboxylic acid tert-butyl ester | 210585-86-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (S)-4-Cyclohexyl-2-hydroxy-pyrrolidine-1-carboxylic acid tert-butyl ester
• CAS: 210585-86-7
• 化学式: C₁₅H₂₇NO₃
• 分子量: 269.384
• InChiKey: XDBJHLOONGMLMV-PZORYLMUSA-N

物化性质

• 沸点：
  374.7±35.0 °C(Predicted)
• 密度：
  1.103±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.14
• 重原子数：
  19.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  49.77
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  三甲基氰硅烷 、 (S)-4-Cyclohexyl-2-hydroxy-pyrrolidine-1-carboxylic acid tert-butyl ester 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (2S,4S)-1-(tert-butyloxycarbonyl)-2-cyano-4-cyclohexylpyrrolidine 、 (2R,4S)-1-(tert-butyloxycarbonyl)-2-cyano-4-cyclohexylpyrrolidine
  参考文献：
  名称：

  Steric and Electronic Influences on the Diastereoselectivity of the Rh₂(OAc)₄-Catalyzed C−H Insertion in Chiral Ester Diazoanilides:  Synthesis of Chiral, Nonracemic 4-Substituted 2-Pyrrolidinones

  摘要：

  A series of N-substituted N-(4-methoxyphenyl)-alpha-(alkoxycarbonyl)-alpha-diazoacetanilides, 10 and ent-10, wherein the alkoxy unit is a chiral auxiliary group [(-)-7 or (+)-8)], was prepared. The Rh-2(OAc)(4)-catalyzed intramolecular C-H insertion reaction of 10 and ent-10, under optimized reaction conditions, was investigated as a route for the preparation of chiral, nonracemic 4-substituted 2-pyrrolidinones. The cyclization reaction led only to 2-pyrrolidinone and 2-azetidinone products; the former products were obtained as major and, in a few cases, as exclusive products. The type and nature of the N-substituent in 10 or ent-10 was found to govern the diastereoselectivity of the reaction. With N-alkyl groups, steric effects play an important role in determining the diastereoselectivity of the reaction. However, with N-arylethyl substituents, electronic effects transmitted by the aryl substituents influenced the diastereoselectivity of the C-H insertion reaction. Specifically, electron-donating substituents were found to markedly attenuate the diastereoselectivity of the reaction. The diastereoselectivity of the reaction ranged from moderate to high (37-98%). A transition-state model to explain the observed diastereoselectivity is provided. The synthetic utility of the method is demonstrated by the stereoselective synthesis of the medicinally important, unnatural amino acid trans-4-cyclohexyl-L-proline 23.

  DOI：

  10.1021/jo971540q
• 作为产物：
  描述：

  二碳酸二叔丁酯 在 4-二甲氨基吡啶 、 双氧水 、 三乙基硼氢化锂 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 18.5h， 生成 (S)-4-Cyclohexyl-2-hydroxy-pyrrolidine-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Steric and Electronic Influences on the Diastereoselectivity of the Rh₂(OAc)₄-Catalyzed C−H Insertion in Chiral Ester Diazoanilides:  Synthesis of Chiral, Nonracemic 4-Substituted 2-Pyrrolidinones

  摘要：

  A series of N-substituted N-(4-methoxyphenyl)-alpha-(alkoxycarbonyl)-alpha-diazoacetanilides, 10 and ent-10, wherein the alkoxy unit is a chiral auxiliary group [(-)-7 or (+)-8)], was prepared. The Rh-2(OAc)(4)-catalyzed intramolecular C-H insertion reaction of 10 and ent-10, under optimized reaction conditions, was investigated as a route for the preparation of chiral, nonracemic 4-substituted 2-pyrrolidinones. The cyclization reaction led only to 2-pyrrolidinone and 2-azetidinone products; the former products were obtained as major and, in a few cases, as exclusive products. The type and nature of the N-substituent in 10 or ent-10 was found to govern the diastereoselectivity of the reaction. With N-alkyl groups, steric effects play an important role in determining the diastereoselectivity of the reaction. However, with N-arylethyl substituents, electronic effects transmitted by the aryl substituents influenced the diastereoselectivity of the C-H insertion reaction. Specifically, electron-donating substituents were found to markedly attenuate the diastereoselectivity of the reaction. The diastereoselectivity of the reaction ranged from moderate to high (37-98%). A transition-state model to explain the observed diastereoselectivity is provided. The synthetic utility of the method is demonstrated by the stereoselective synthesis of the medicinally important, unnatural amino acid trans-4-cyclohexyl-L-proline 23.

  DOI：

  10.1021/jo971540q