N,N-dimethyl-2-(n-butyl)cyclopropene-1-carboxamide

• 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: N,N-dimethyl-2-(n-butyl)cyclopropene-1-carboxamide
• 英文别名: (1R)-2-butyl-N,N-dimethylcycloprop-2-ene-1-carboxamide
• 化学式: C₁₀H₁₇NO
• 分子量: 167.251
• InChiKey: MECUKXGOIPXIJC-SECBINFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  N,N-dimethyldiazoacetamide 、 1-己炔 在 Rh₂(5R-MEPY)₄ 作用下， 以 二氯甲烷 为溶剂， 生成 N,N-dimethyl-2-(n-butyl)cyclopropene-1-carboxamide 、 N,N-dimethyl-2-(n-butyl)cyclopropene-1-carboxamide
  参考文献：
  名称：

  Effective Uses of Dirhodium(II) Tetrakis[methyl 2-oxopyrrolidine-5(R or S)-carboxylate] for Highly Enantioselective Intermolecular Cyclopropenation Reactions

  摘要：

  The title compounds are effective catalysts for intermolecular cyclopropenation reactions of l-alkynes with diazo esters and diazo amides. Diastereoselectivities achieved from the appropriate match with d- or l-menthyl diazoacetate are 77 to greater than or equal to 94% de. Enantioselectivities up to greater than or equal to 94% ee with 3-methoxy-1-propyne and 3,3-diethoxy-1 -propyne have been obtained. Variations in these values for metal carbene additions to alkynes are associated with electronic and/or steric influences from the alkyne or carbene substituents. N,N-Dimethyldiazoacetamide provides a higher level of enantiocontrol than do diazo esters. The absolute configurations of the cyclopropene products have been established; dirhodium(II) tetrakis[methyl 2-oxopyrrolidine-5(S)-carboxylate], Rh-2(5S-MEPY)(4), produces 2-substituted-2-cyclopropene-1-carboxylates having the (S)-configuration whereas use of Rh-2(5R-MEPY)(4) provides these cyclopropene products in the (R)-configuration. Diimide reduction of these cyclopropenecarboxylates produces the cis-disubstituted cyclopropane products exclusively.

  DOI：

  10.1021/ja00098a009

文献信息

• Effective Uses of Dirhodium(II) Tetrakis[methyl 2-oxopyrrolidine-5(R or S)-carboxylate] for Highly Enantioselective Intermolecular Cyclopropenation Reactions
  作者：Michael P. Doyle、Marina Protopopova、Paul Muller、Doina Ene、Evgeny A. Shapiro

  DOI：10.1021/ja00098a009

  日期：1994.9

  The title compounds are effective catalysts for intermolecular cyclopropenation reactions of l-alkynes with diazo esters and diazo amides. Diastereoselectivities achieved from the appropriate match with d- or l-menthyl diazoacetate are 77 to greater than or equal to 94% de. Enantioselectivities up to greater than or equal to 94% ee with 3-methoxy-1-propyne and 3,3-diethoxy-1 -propyne have been obtained. Variations in these values for metal carbene additions to alkynes are associated with electronic and/or steric influences from the alkyne or carbene substituents. N,N-Dimethyldiazoacetamide provides a higher level of enantiocontrol than do diazo esters. The absolute configurations of the cyclopropene products have been established; dirhodium(II) tetrakis[methyl 2-oxopyrrolidine-5(S)-carboxylate], Rh-2(5S-MEPY)(4), produces 2-substituted-2-cyclopropene-1-carboxylates having the (S)-configuration whereas use of Rh-2(5R-MEPY)(4) provides these cyclopropene products in the (R)-configuration. Diimide reduction of these cyclopropenecarboxylates produces the cis-disubstituted cyclopropane products exclusively.