叔丁基自由基引发的1,2-炔基迁移反应研究  

Study on tert-Butyl Radical-Initiated 1,2-Alkynyl Migration

作　　者：张萍 张天舒[1] 蔡佩君 姜波[2] 屠树江 Zhang Ping;Zhang Tianshu;Cai Peijun;Jiang Bo;Tu Shujiang(School of Chemical Engineering and Technology,China University of Mining and Technology,Xuzhou,Jiangsu 221116;School of Chemistry and Materials Science,Jiangsu Normal University,Xuzhou,Jiangsu 221116;Jiangsu Provincial Xuzhou Pharmaceutical Vocational College,Xuzhou,Jiangsu 221116)

机构地区：[1]中国矿业大学化工学院,江苏徐州221116 [2]江苏师范大学化学与材料科学学院,江苏徐州221116 [3]江苏省徐州医药高等职业学校,江苏徐州221116

出　　处：《有机化学》2021年第6期2408-2416,共9页Chinese Journal of Organic Chemistry

基　　金：中央高校基本科研专项资金基金(No.JH180263)资助项目。

摘　　要：报道了一类由叔丁基自由基引发的1,2-炔基迁移反应.该反应利用特戊醛在二叔丁基过氧化物(DTBP)介导下能产生叔丁基自由基的特性,将其与1,4-烯炔底物发生自由基加成及炔基迁移过程,合成了一系列α-炔基酮化合物,产率优良,实现了非活化烯烃的烷基炔基化.基于实验结果及文献报道,提出了可能的反应机理,涉及叔丁基自由基激发的自由基加成、反"鲍德温"规则的3-exo-dig环化及炔基迁移过程.该反应具有官能团兼容性高、无需金属催化剂及操作简便等优点,为非活化烯烃的双官能团化提供了一种有效的策略.A new tert-butyl radical-induced 1,2-alkynyl migration reaction is reported.By using the characteristics of in-situ-generation of tert-butyl radical from pivalaldehyde mediated by di-tert-butyl peroxide(DTBP),tert-butyl radical-triggered addition and alkynyl migration of the preformed 1,4-enynes led to the synthesis of a series ofα-alkynyl ketones with good to excellent yields,thereby realizing alkylalkynylation of unactivated olefins.Based on the experimental results and literature reports,a possible reaction mechanism is proposed,which involves tert-butyl radical-triggered addition,3-exo-dig cyclization of anti-"Baldwin"rule and alkynyl migration process.This reaction has the advantages of high functional group compatibility,metal-free conditions,and simple operation,which provides a feasible and effective synthetic strategy for the bifunctionalization of unactivated olefins.

关 键 词：炔基迁移 1 4-烯炔 双官能团化 反鲍德温规则 

分 类 号：O621.25[理学—有机化学]