(S,E)-3-(2-chlorophenyl)-5-(2-oxo-5-phenylfuran-3(2H)-ylidene)-5-phenylpentanal | 1435460-23-3

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 木脂素内酯
• 英文名称: (S,E)-3-(2-chlorophenyl)-5-(2-oxo-5-phenylfuran-3(2H)-ylidene)-5-phenylpentanal
• 英文别名: (3S,5E)-3-(2-chlorophenyl)-5-(2-oxo-5-phenylfuran-3-ylidene)-5-phenylpentanal
• CAS: 1435460-23-3
• 化学式: C₂₇H₂₁ClO₃
• 分子量: 428.915
• InChiKey: XVSLQHSFIBNTPL-VANSDEMISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-chlorocinnamaldehyde 、 5-phenyl-3-(1-phenylethylidene)furan-2-one 在 (S)-2-(((叔丁基二甲基甲硅烷基)氧基)二苯基甲基)吡咯烷 、 N,N-二异丙基乙胺 、 sodium chloride 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 18.0h， 以89%的产率得到(S,E)-3-(2-chlorophenyl)-5-(2-oxo-5-phenylfuran-3(2H)-ylidene)-5-phenylpentanal
  参考文献：
  名称：

  Beyond Classical Reactivity Patterns: Shifting from 1,4- to 1,6-Additions in Regio- and Enantioselective Organocatalyzed Vinylogous Reactions of Olefinic Lactones with Enals and 2,4-Dienals

  摘要：

  Organocatalysis is shown to expand the classical reactivity pattern for conjugate addition reactions. It is demonstrated that the site selectivity can be extended from 1,4- to 1,6 additions for the enantioselective vinylogous additions of methyl-substituted vinylogous lactones to enals and 2,4-dienals. This novel reactivity is demonstrated for methyl-substituted olefinic azlactones and butyrolactones. Their synthetic potential is first highlighted by the development of the organocatalytic regioselective vinylogous 1,4-addition to enals which proceeds with a very high level of double bond geometry control and excellent enantioselectivity. The concept is developed further for the unprecedented intermolecular enantioselective organocatalyzed vinylogous 1,6 addition to linear 2,4-dienals, by which the site selectivity of the process is extended from the beta-position to the remote delta-position of the 2,4-dienal. The organocatalyst controls the newly generated stereocenter six bonds away from the stereocenter of the catalyst with a high level of enantiocontrol, and the products are obtained with full control of double bonds configuration. The scope of these new reaction concepts is demonstrated for a series of aliphatic and aryl substituted enals and 2,4-dienals undergoing enantioselective vinylogous reactions with methyl substituted olefinic azlactones and butyrolactones. Furthermore, mechanistic considerations are presented which can account for the change from 1,4- to 1,6 selectivity Finally, a number of different transformations of the optically active 1,4- and 1,6 addition products are demonstrated.

  DOI：

  10.1021/ja4029928

文献信息

• Beyond Classical Reactivity Patterns: Shifting from 1,4- to 1,6-Additions in Regio- and Enantioselective Organocatalyzed Vinylogous Reactions of Olefinic Lactones with Enals and 2,4-Dienals
  作者：Luca Dell’Amico、Łukasz Albrecht、Tricia Naicker、Pernille H. Poulsen、Karl Anker Jørgensen

  DOI：10.1021/ja4029928

  日期：2013.5.29

  Organocatalysis is shown to expand the classical reactivity pattern for conjugate addition reactions. It is demonstrated that the site selectivity can be extended from 1,4- to 1,6 additions for the enantioselective vinylogous additions of methyl-substituted vinylogous lactones to enals and 2,4-dienals. This novel reactivity is demonstrated for methyl-substituted olefinic azlactones and butyrolactones. Their synthetic potential is first highlighted by the development of the organocatalytic regioselective vinylogous 1,4-addition to enals which proceeds with a very high level of double bond geometry control and excellent enantioselectivity. The concept is developed further for the unprecedented intermolecular enantioselective organocatalyzed vinylogous 1,6 addition to linear 2,4-dienals, by which the site selectivity of the process is extended from the beta-position to the remote delta-position of the 2,4-dienal. The organocatalyst controls the newly generated stereocenter six bonds away from the stereocenter of the catalyst with a high level of enantiocontrol, and the products are obtained with full control of double bonds configuration. The scope of these new reaction concepts is demonstrated for a series of aliphatic and aryl substituted enals and 2,4-dienals undergoing enantioselective vinylogous reactions with methyl substituted olefinic azlactones and butyrolactones. Furthermore, mechanistic considerations are presented which can account for the change from 1,4- to 1,6 selectivity Finally, a number of different transformations of the optically active 1,4- and 1,6 addition products are demonstrated.