Photocatalytic[3+2]Cycloaddition of Alkyl/aryl Iodides and Internal Alkynes by Merging Halogen and Hydrogen Atom Transfer  

作　　者：Zhenyu Gu Rong Jia Tianqing Zeng Hanliang Zheng Gangguo Zhu 

机构地区：[1]Key Laboratory of the Ministry of Education for Advanced Catalysis Materials,College of Chemistry and Materials Science,Zhejiang Normal University,688 Yingbin Road,Jinhua,Zhejiang 321004,China

出　　处：《Chinese Journal of Chemistry》2024年第19期2329-2334,共6页中国化学（英文版）

基　　金：supported by the Natural Science Foundation of Zhejiang Province(LZ20B020001 and LY23B020004);the Ten Thousand Talents Plan of Zhejiang Province(2020R52021);the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang Province(2022R01007);the National Natural Science Foundation of China(22371262,22071218,and 22203076).

摘　　要：Comprehensive Summary A visible light photocatalytic[3+2]cycloaddition of alkynes with readily accessible organic iodides as the C3 synthon is developed herein.By merging halogen atom transfer(XAT)and hydrogen atom transfer(HAT),alkyl/aryl iodides serve as a formal diradical precursor and add across C-C triple bonds to deliver a number of functionalized cyclopentanes in moderate to high yields with exceptional regio-and diastereoselectivity.A reductive radical-polar crossover mechanism,involving the cascade XAT,radical addition,1,5-HAT,polar effect-promoted 5-endo annulation,single electron transfer(SET)reduction,and protonation,may account for this unprecedented dehalogenative[3+2]cycloaddition.This work not only expands the repertoire of the traditional RATC methodology,but also provides a robust platform for the expedient assembly of cyclopentanes,a valuable structural motif in the realms of medicinal chemistry and material sciences.

关 键 词：Photocatalysis Halogen atom transfer Hydrogen atom transfer [3+2]cycloaddition CYCLOPENTANE Carbocycles Radical reactions DIASTEREOSELECTIVITY 

分 类 号：O64[理学—物理化学]