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综述

丰产金属催化烯基金属试剂的不对称烯基化反应研究进展

吴良a, 魏瀚林a, 申杰峰*,a, 陈建中*,b, 张万斌a,b   

  1. a上海交通大学药学院 变革性分子前沿科学中心 上海市手性药物分子工程重点实验室 上海 200240;
    b上海交通大学化学化工学院 上海 200240
  • 通讯作者: *E-mail: sjfhx@163.com, 0091109001@sju.edu.cn
  • 作者简介:吴良, 2020年在上海交通大学获得博士学位(导师: 张万斌 教授). 目前在上海交通大学张万斌教授课题组从事博士后研究工作, 主要研究方向为丰产金属催化的不对称反应.申杰峰,博士,上海交通大学药学院副研究员,硕士研究生导师. 2012博士毕业于上海交通大学化学化工学院(导师:张万斌 教授);同年进入上海交通大学药学院从事博士后研究工作(导师:刘燕刚 教授). 2014年至今就职于上海交通大学药学院,主要研究方向为不对称催化、化学工艺及新药开发研究.陈建中,上海交通大学化学化工学院副研究员. 本科毕业于浙江工业大学;硕士毕业于华东理工大学(导师:赵敏 副教授);博士毕业于上海交通大学(导师:张万斌 教授),同年本校从事博士后研究(导师: 颜德岳 院士). 自2015年起在上海交通大学主要从事不对称反应研究,新型配体的设计、合成及应用,药物和香料等合成工艺研究等.
  • 基金资助:
    上海市“超级博士后”激励计划(No. 2020272)和国家自然科学基金(No. 21620102003, 21772119, 21831005)资助项目.

Development of Earth-Abundant Transition Metals-Catalyzed Enantioselective Alkenylations using Alkenyl Metal Nucleophiles

Wu, Lianga, Wei, Hanlina, Shen, Jiefenga,*, Chen, Jianzhongb,*, Zhang, Wanbina,b   

  1. aShanghai Key Laboratory for Molecular Engineering and Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Pharmacy, Shanghai Jiao Tong University, Shanghai, 200240;
    bSchool of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240
  • Supported by:
    Shanghai Post-Doctoral Excellence Program (No. 2020272), and National Natural Science Foundation of China (No. 21620102003, 21772119, 21831005).

烯丙位手性中心不仅广泛存在于天然产物和药物活性分子中,也是有机合成中的重要合成砌块。过渡金属催化的烯基金属试剂作为亲核试剂的不对称加成或偶联反应是构建这一结构的非常有吸引力的策略之一。在众多金属催化剂中,铁钴镍铜等丰产金属由于其独特的催化活性以及低毒性、环境友好等优点而被用来代替铑钯等稀有金属应用于此类不对称烯基化反应中,并取得了显著的成果。基于此,本文将综述丰产金属催化的烯基金属试剂参与的不对称烯基化反应研究进展。主要包括,1)钴催化的不对称烯基化反应、2)镍催化的不对称烯基化反应、3)铜催化的不对称烯基化反应、以及4)其他丰产金属催化的不对称烯基化反应等四部分。

关键词: 丰产金属催化, 烯基金属试剂, 不对称烯基化, 不对称加成, 不对称偶联

Allylic chiral centers are widely present in natural products and pharmaceutically active molecules, and play a vital role in the construction of organic compounds through pericyclic reactions, oxidations or reductions and other transformations. The transition metal-catalyzed asymmetric addition or coupling reaction using alkenyl metal nucleophiles is one of the most attractive strategies for the synthesis of these structures. Among the many metal catalysts, earth-abundant transition metals such as iron, cobalt, nickel and copper have been used to replace precious metals such as rhodium and palladium, and have gained attention for use in enantioselective alkenylations. Indeed, remarkable advances have been achieved with these catalysts due to their unique catalytic activity, low toxicity, and environmentally friendliness. The 3d metals are known to undergo facile one electron oxidation state changes often with associated spin state complexity, uncontrolled reactions with dioxygen, and facile ligand redistribution. In the reaction process, the earth-abundant transition metals have the ability to undergo two-electron transfer and single-electron transfer processes, therefore they have more valence changes and catalytic pathways which can be exploited. Based on this, this article will review the latest research in earth-abundant transition metal-catalyzed enantioselective alkenylation using alkenyl metal nucleophiles. It is divided into four sections consisting of cobalt-catalyzed enantioselective alkenylations using alkenyl metal reagents, nickel-catalyzed enantioselective alkenylations using alkenyl metal reagents, copper-catalyzed enantioselective alkenylations using alkenyl metal reagents, and other earth-abundant transition metals catalyzed enantioselective alkenylations using alkenyl metal reagents.

Key words: earth-abundant metal catalysis, alkenyl metal reagents, enantioselective alkenylation, asymmetric addition, asymmetric coupling