(S)-(+)-4-cyclohexyl-1-(4-methoxyphenyl)-2-pyrrolidinone | 174618-42-9

• 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: (S)-(+)-4-cyclohexyl-1-(4-methoxyphenyl)-2-pyrrolidinone
• 英文别名: (4S)-4-cyclohexyl-1-(4-methoxyphenyl)pyrrolidin-2-one
• CAS: 174618-42-9
• 化学式: C₁₇H₂₃NO₂
• 分子量: 273.375
• InChiKey: YLIHJKDWDOSILR-CQSZACIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 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：

  (S)-(+)-4-cyclohexyl-1-(4-methoxyphenyl)-2-pyrrolidinone 在 4-二甲氨基吡啶 、 ammonium cerium(IV) nitrate 、 三氟化硼乙醚 、 双氧水 、 三乙基硼氢化锂 、 三乙胺 作用下， 以 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 21.0h， 生成 (2S,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：

  3-[N-(2-cyclohexylethyl)-4-methoxyanilino]-3-oxopropanoic acid 在 dirhodium tetraacetate 、 potassium hydride 、 甲烷磺酰基叠氮化物 、 sodium chloride 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 二甲基亚砜 为溶剂， 生成 (S)-(+)-4-cyclohexyl-1-(4-methoxyphenyl)-2-pyrrolidinone
  参考文献：
  名称：

  Rh 2（OAc）4催化CH在手性酯重氮苯胺中的插入

  摘要：

  研究了Rh 2（OAc）4催化的手性酯重氮苯胺化物中的CH插入反应，发现该化合物在脱碳烷氧基化后可产生具有中等至较高ee（37-98％）的4-取代的2-吡咯烷酮。发现在影响N-芳基乙基重氮苯胺中反应的对映选择性方面，电子效应与空间效应相反。

  DOI：

  10.1016/0040-4039(95)02115-9

文献信息

• The Rh2(OAc)4 catalysed CH insertion in chiral ester diazoanilides
  作者：Andrew G.H. Wee、Baosheng Liu

  DOI：10.1016/0040-4039(95)02115-9

  日期：1996.1

  The Rh2(OAc)4 -catalysed CH insertion reaction in chiral ester diazoanilides was investigated and was found to yield 4-substituted 2-pyrrolidinones with moderate to high e.e. (37–98 %) after decarbalkoxylation. Electronic effects were found to oppose steric effects in influencing the enantioselectivity of the reaction in N-arylethyl diazoanilides.

  研究了Rh 2（OAc）4催化的手性酯重氮苯胺化物中的CH插入反应，发现该化合物在脱碳烷氧基化后可产生具有中等至较高ee（37-98％）的4-取代的2-吡咯烷酮。发现在影响N-芳基乙基重氮苯胺中反应的对映选择性方面，电子效应与空间效应相反。
• 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
  作者：Andrew G. H. Wee、Baosheng Liu、Douglas D. McLeod

  DOI：10.1021/jo971540q

  日期：1998.6.1

  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.