有机化学 ›› 2017, Vol. 37 ›› Issue (7): 1589-1612.DOI: 10.6023/cjoc201704017 上一篇    下一篇

所属专题: 热点论文合辑

综述与进展

过渡金属催化的有机硼试剂对亚胺的不对称加成研究进展

陈雕, 徐明华   

  1. 中国科学院上海药物研究所 新药研究国家重点实验室 上海 201203
  • 收稿日期:2017-04-12 修回日期:2017-05-02 发布日期:2017-05-10
  • 通讯作者: 徐明华 E-mail:xumh@simm.ac.cn
  • 基金资助:

    国家自然科学基金(Nos.21325209,21472205)、上海市优秀学术带头人计划(No.14XD1404400)资助项目.

Transition Metal-Catalyzed Asymmetric Addition of Organoboron Reagents to Imines

Chen Diao, Xu Ming-Hua   

  1. State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203
  • Received:2017-04-12 Revised:2017-05-02 Published:2017-05-10
  • Contact: 10.6023/cjoc201704017 E-mail:xumh@simm.ac.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos.21325209,21472205) and the Program of Shanghai Academic Research Leaders (No.14XD1404400).

手性胺是有机合成中一类非常重要的合成砌块,在天然产物、生物活性分子及药物分子中广泛存在,因此发展高效的构建手性胺类化合物的方法,一直都是合成有机化学家们关注的重点.有机硼试剂近年来以其低毒、稳定、易得等优点逐渐受到合成化学家的青睐,被越来越多地用于过渡金属催化的反应中.本文综述了近十多年来基于手性辅剂及手性催化策略的过渡金属催化的有机硼试剂对亚胺的不对称加成研究进展,着重探讨了各种手性配体在反应中的应用以及α-手性胺类化合物的立体选择性构建.

关键词: 不对称合成, 手性胺, 金属催化, 不对称加成, 有机硼试剂

Chiral amines are important building blocks in organic synthesis, they also present in numerous natural products, biologically active compounds and pharmaceutical agents. In recent years, the use of various organoboron reagents in transition metal-catalyzed reactions has attracted considerable attentions because of their ready avilibility, low toxicity, good air and moisture stability as well as high functional group compatibility. This review summarizes the remarkable progress and advances in transition metal-catalyzed asymmetric addition of organoboron reagents to imines over the past few years, providing an overview of the recent achievements in stereoselective synthesis of α-chiral amines by using chiral auxiliary or chiral catalysis strategies. At the present time, rhodium-based asymmetric catalysis has proven to be the most efficient and reliable approach to furnish highly optically active α-chiral amines. Varieties of chiral ligands including monophosphines, biphosphines, amidomonophosphanes, phosphoramidites, phosphites, dienes, sulfur-olefins, phosphorus-olefins have showed the great potential in many asymmetric additions of organoboron reagents to imines, enabling the access of both secondary and tertiary α-chiral amines with good to excellent enantioselectivities. On the other hand, important progress has been made in developing effective palladium catalysts mainly based on chiral pyridine-oxazoline and phosphine-oxazoline ligands. However, future studies in this area towards the objective of developing more efficient, practical and general methods remain challenging.

Key words: asymmetric synthesis, chiral amine, metal catalysis, asymmetric addition, organoboron