利用自由基引发的1,2-炔基迁移实现非活性烯烃的炔膦酰化  

Alkynylphosphonation of Unactivated Olefins via Radical-Triggered 1,2-Alkynyl Migration

作　　者：张萍 石浩楠[2] 张天舒 蔡佩君 姜波[2] 屠树江 Zhang Ping;Shi Haonan;Zhang Tianshu;Cai Peijun;Jiang Bo;Tu Shujiang(School of Chemical Engineering&Technology,China University of Mining and Technology,Xuzhou,Jiangsu 221116;School of Chemistry&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》2020年第2期423-431,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：研究了1,4-烯炔衍生物与二芳基膦氧化物在银介导下发生的炔酰化反应.该反应利用自由基引发的1,2-炔基迁移策略合成了一系列γ-酮膦氧化物,产率适中.该反应机理可能涉及膦中心自由基与乙烯基的加成、3-exo-dig环化和1,2-炔基迁移等连续的过程,一步形成了C-P、C-C键等化学键,实现了非活性烯烃的双官能化.A silver-mediated alkynylphosphonation of 1,4-enynes with diarylphosphine oxides has been developed, by which a wide range of γ-ketophosphine oxides with moderate to good yields were synthesized through radical 1,2-alkynyl migration. The transformation proceeded with sequential P-centered radical addition to vinyl unit, 3-exo-dig cyclization and 1,2-alkynyl migration, resulting in the bond-forming events including C-P and C-C bonds to realize difunctionalization of unactivated olefins.

关 键 词：1 4-烯炔衍生物 炔膦酰化反应 γ-酮膦氧化物 炔基迁移 自由基化学 

分 类 号：O621.25[理学—有机化学]