Catalytic Enantioselective Construction of Chiral Benzo-Fused N-Heterocycles through Friedel-Crafts-Type Electrophilic Chlorination

作     者：Jie Luo Yuanyuan Zhang Fuming Zhong Xiaodan Zhao 

作者机构：Institute of Organic Chemistry and MOE Key Laboratory of Bioinorganic and Synthetic ChemistrySchool of ChemistrySun Yat-sen UniversityGuangzhou 510275 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2022年第4卷第5期

页      面：1486-1498页

学科分类：07[理学] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：the National Natural Science Foundation of China(grant nos.91856109 and 21772239) the Fundamental Research Funds for the Central Universities(grant no.20lgzd21) the Leading Scientific,Technical and Innovation Talents of Guangdong Special Support Program(grant no.2019TX05Y638)for financial support. 

主　　题：benzo-fused N-heterocycles asymmetric synthesis chiral sulfide catalysis electrophilic chlorination dearomatization divergent reactions 

摘      要：Chiral benzo-fused N-heterocycles are frequently found in natural and synthetic products.However,their synthesis usually suffers from different limitations such as difficulty in accessing appropriate starting materials and unsatisfactory stereoselectivities.In this work,an unprecedented chiral sulfide-catalyzed enantioselective Friedel-Crafts-type electrophilic chlorination is shown to construct various 3,4-functionalized tetrahydroquinolines with excellent enantio-and diastereoselectivities from readily available aniline derivatives.Interestingly,employing N-allyl 1-naphthanilides as substrates,divergent reactions via chlorocarbocyclization and dearomatization occurred to afford two chiral polycyclic benzo-fused N-heterocycles.The system that we developed extends the scope of asymmetric chlorination to general substrateswithout the need of a N-H group,and significantly promotes the synthesis of enantioenriched benzo-fused N-heterocycles.