氮杂环磷氢试剂的氢转移活性研究进展  

Recent Advances in Hydrogen Transfer Reactivities of N-Heterocyclic Phosphines

作　　者：张雨杉 桓臻 杨金东 程津培[1,2,3] Yushan Zhang;Zhen Huan;Jindong Yang;Jinpei Cheng(Center of Basic Molecular Science,Department of Chemistry,Tsinghua University,Beijing 100084;State Key Laboratory of Elemento-organic Chemistry,College of Chemistry,Nankai University,Tianjin 300071;Haihe Laboratory of Sustainable Chemical Transformations,Tianjin 300192)

机构地区：[1]清华大学化学系基础分子科学中心,北京100084 [2]南开大学化学学院元素有机化学国家重点实验室,天津300071 [3]物质绿色创造与制造海河实验室,天津300192

出　　处：《有机化学》2023年第11期3806-3825,共20页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.22222106,21973052,22193011和21933008);物质绿色创造与制造海河实验室资助项目。

摘　　要：氮杂环磷氢(NHP-H)独特的杂环骨架赋予了其优异的负氢还原能力.过去十年间,NHP-H被广泛用于极性不饱和底物的负氢还原中.近年来,随着自由基化学的兴起,其在催化自由基还原领域崭露头角,方兴未艾.这种新的NHP-H反应模式有望突破负氢机理对底物极性的限制,可大大拓展底物的适用范围.简要总结了NHP-H在负氢还原和自由基还原中的合成应用,重点关注其自由基反应相关的性质,包括NHP自由基及其前体的结构、性质、合成应用等.The unique heterocyclic skeletons of N-heterocyclic phosphines(NHP-H)endow them with excellent hydridic reactivity,which have enabled a great array of catalytic hydrogenations of unsaturated substrates in the past decade.Recently,applications of NHP-H in radical reductions,especially in a catalytic fashion,have emerged as a promising forefront area.This new reaction pattern,distinctive from but complementary to the well-established hydride pathway,can greatly expand the reaction scope toσ-bond scission.Herein,some representative examples of synthetic applications of NHP-H in both hydridic and radical reductions with emphasis on their radical reactivity are briefly summarized,including the structural and property studies of NHP radicals and their precursors as well as their applications in radical hydrogenations.

关 键 词：氮杂环磷氢 有机催化 自由基活性 负氢还原 构效关系 

分 类 号：O626[理学—有机化学]