可见光驱动酚/芳胺联-1,6-烯炔与全卤代甲烷的Kharasch反应  

Visible-Light-Driven Photocatalytic Kharasch Reaction of Phenol/Arylamine-Linked 1,6-Enynes with Perhalogenated Methane

作　　者：季晓霜 付荣 王树良 郝文娟 姜波 Ji Xiaoshuang;Fu Rong;Wang Shuliang;Hao Wenjuan;Jiang Bo(School of Chemistry&Materials Science,Jiangsu Normal University,Xuzhou,Jiangsu 221116)

机构地区：[1]江苏师范大学化学与材料科学学院,江苏徐州221116

出　　处：《有机化学》2022年第12期4282-4291,共10页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21971090)资助项目。

摘　　要：1,n-烯炔合成子参与的涉及原子转移过程的自由基环化碳卤官能化是一类有效且实用的方法,它通过利用原子转移试剂中碳卤σ键的自由基龟裂及其在烯炔母核π键上的移位来实现卤代环系结构的有序构建,展现了完全原子经济性.近年来,该类反应成为研究热点之一.报道了一类通用可见光催化的酚/芳胺联-1,6-烯炔和全卤代甲烷(如三氯溴甲烷或四溴化碳)参与的环化碳卤官能团化反应,在温和且无氧化剂条件下原子经济且高效地合成了一系列作为主要立体异构体的(Z)-2,3-二氢苯并呋喃和(Z)-吲哚啉衍生物,收率优良,其中大部分产物仅以(Z)-构型被合成.该反应具有底物范围广、官能团耐受性高、高原子经济以及高立体选择性等优点,为2,3-二氢苯并呋喃和吲哚啉杂环的合成提供一类绿色、原子经济、高效的合成策略.Radical annulative carbohalofunctionalization of 1,n-enynes via atom transfer processes constitutes an efficient and practical synthetical strategy for accessing halogenated cyclic structures with complete atom economy through radical cleavage of a pre-existing carbon-halogenσ-bond of an atom transfer reagent and their transposition over theπ-bond of enyne motifs.Recently,such reaction has become one of hot topics.A general photocatalytic annulative carbohalogenation of phenol/arylamine-linked 1,6-enynes with perhalogenated methanes such as BrCCl3 or CBr4 is disclosed,leading to the atom-economic,efficient synthesis of functionalized(Z)-2,3-dihydrobenzofurans and(Z)-indolines as main stereoisomers with good yields and high stereoselectivity under mild and oxidant-free conditions,in which only(Z)-configuration was observed in most products.This protocol demonstrates wide substrate scope,high functional group tolerance,and high atom economy as well as high stereoselectivity,providing a green,atom-economic and efficient method toward 2,3-dihydrobenzofurans and indolines.

关 键 词：可见光催化反应 环化碳卤官能化反应 原子经济性 2 3-二氢苯并呋喃衍生物 

分 类 号：O626[理学—有机化学]