### 过渡金属与光氧化还原协同催化的烯丙基取代反应的研究进展

1. 南京大学化学化工学院 生命分析化学国家重点实验室 南京 210023
• 收稿日期:2019-05-14 出版日期:2019-09-15 发布日期:2019-07-16
• 通讯作者: 俞寿云 E-mail:yushouyun@nju.edu.cn
• 作者简介:张洪浩, 1991年出生于江苏扬州, 2009年和2013年于江苏师范大学先后获得学士和硕士学位, 2013年至今在俞寿云教授指导下攻读博士学位. 其研究兴趣主要是可见光促进的不对称催化反应.|俞寿云, 1978年11月出生于江苏南京. 2001年获南京大学理学学士学位. 2006年获中国科学院上海有机化学研究所理学博士学位(导师为马大为研究员). 2006年到2007年留所任助理研究员. 2007年-2010年在美国宾夕法尼亚大学进行博士后研究(合作导师Jeffrey W. Bode教授). 2010年9月被聘为南京大学化学化工学院副教授, 博士生导师. 2016年起任南京大学化学化工学院教授. 曾获2012年Thieme Chemistry Journals Award, 2007年国家自然科学二等奖(排名第四)和2005年上海市科技进步一等奖(排名第四)等奖项.
• 基金资助:
项目受国家自然科学基金重点项目资助(No. 21732003)

### Advances on Transition Metals and Photoredox Cooperatively Catalyzed Allylic Substitutions

Zhang, Hong-Hao, Yu, Shouyun*()

1. State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering,Nanjing University, Nanjing 210023
• Received:2019-05-14 Online:2019-09-15 Published:2019-07-16
• Contact: Yu, Shouyun E-mail:yushouyun@nju.edu.cn
• Supported by:
Project supported by the National Natural Science Foundation of China(No. 21732003)

Allylic substitutions catalyzed by transition metals are important and practical reactions, which can construct carbon-carbon bonds and carbon-heteroatom bonds efficiently and stereoselectively. Various transition metal catalysts, such as Pd, Ir, Cu, Ni, Rh and Ru, have been widely used in this reaction. To date, various “soft”, or stabilized nucleophiles (pKa<25), including malonates, acetoacetates and enolates, have been used in allylic substitutions. Conversely, the high reactivity of “hard”, or non-stabilized alkyl nucleophiles (pKa>25) has limited their utility in catalytic processes and their compatibility with functional groups. Visible light photoredox catalysis has been widely used in organic synthesis because it can generate high reactive intermediates, such as free radicals and radical ions, under mild conditions using green and clean energy, and has gradually developed into an important synthetic tool. Furthermore, merging photoredox catalysis with transition metal catalysts has become a popular strategy for expanding the synthetic utility of visible-light photocatalysis, and has led to the discovery of novel reaction modes. Due to the high activity of the intermediates in photoredox catalysis, the selectivity of these reactions, especially stereoselectivity, is still a challenge. In view of the importance of allyl substitutions, the allyl substitution co-catalyzed by transition metals and photoredox has attracted the interest of chemists. The synergistic strategy can realize allylic substitutions which are difficult to be achieved by single transition metal catalysis. The regioselectivity and stereoselectivity of these reactions also show different characteristics. It is expected to become an important complement to allylic substitution catalyzed by single metal. In this review, recent advances on allylic substitution co-catalyzed by different transition metals and photoredox are summarized. Meanwhile, the mechanism of representative transformations will be briefly introduced and the prospective in this area will be given.