化学学报 ›› 2016, Vol. 74 ›› Issue (2): 130-148.DOI: 10.6023/A15090617 上一篇    下一篇

综述

亲核叔膦促进的联烯酸酯环加成反应研究进展

杨丽军, 马军安   

  1. 天津大学化学系 天津化学化工协同创新中心 天津 300072
  • 收稿日期:2015-09-22 出版日期:2016-02-15 发布日期:2016-02-22
  • 通讯作者: 马军安 E-mail:majun_an68@tju.edu.cn
  • 基金资助:

    项目受国家自然科学基金(Nos.21225208,21532008)、国家基础研究项目(973课题,No.2014CB745100)及天津市科委项目(No.14JCZDJC33400)资助.

New Advances on Nucleophilic Phosphine-Triggered Annulation Reactions of Allenoates

Yang Lijun, Ma Junan   

  1. Department of Chemistry, Tianjin University and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072
  • Received:2015-09-22 Online:2016-02-15 Published:2016-02-22
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21225208, 21532008), the National Basic Research Program of China (973 Program, No. 2014CB745100), and Tianjin Municipal Science & Technology Commission (No. 14JCZDJC33400).

20世纪90年代中期,陆熙炎教授报道了亲核叔膦促进的联烯酸酯与缺电子烯烃和亚胺环加成反应.二十年来,作为高效构建功能化碳环及杂环化合物方法,叔膦促进的联烯酸酯环加成反应的发展和应用受到化学家的广泛关注.多样性的亲核叔膦和不同结构联烯酸酯的引入,可呈现多种类型的环加成反应.特别是手性叔膦的应用,高选择性地实现了对该类反应的不对称催化,为一些天然产物和药物模块的全合成开辟了新途径.此外,醛酮化合物也被运用到此类反应中,构建了多种有用的含氧杂环.本篇综述包括六部分:第一部分是引言,概括介绍陆氏反应;第二至五部分分别阐述了亲核叔膦促进联烯酸酯与缺电子烯烃、亚胺、醛酮以及特定亲核试剂的各种环加成反应;最后一部分是总结与展望.

关键词: 亲核叔膦, 联烯酸酯, 环加成反应, 陆氏反应, 两性离子中间体

In the mid 1990s, Lu and co-workers reported the nucleophilic phosphine-triggered annulation reactions of allenoates with electron-deficient olefins or imines. As one of the most efficient and straightforward synthetic strategies for the construction of highly functionalized carbocycle or heterocycle structural motifs, the development and application of nucleophilic phosphine-triggered annulation of allenoates by using various nucleophilic phosphines and electron-deficient partners have attracted more and more interests of chemists over the past decades. Furthermore, the development of asymmetric phosphine-triggered annulation of allenoates cleaved a new way to the total synthesis of bioactive natural products and medicinally important substances. In addition, aldehydes and ketones were also employed into this reaction, leading to a wide range of O-fused heterocycles. This review focuses on the important developments concerning racemic and asymmetric annulation reactions of allenoates in the past two decades.

Key words: nucleophilic phosphine, allenoate, annulation reaction, Lu Reaction, zwitterionic intermediate