(二氟甲基)三甲基硅烷试剂参与的二氟甲基化反应  

Progress in the study of difluoromethylation reactions with TMSCF_(2)H reagent

作　　者：陈定奔 高翔[2] 宋绍睿[2] 寇敏 倪传法 胡金波[1] Dingben Chen;Xiang Gao;Shaorui Song;Min Kou;Chuanfa Ni;Jinbo Hu(Key Laboratory of Organofluorine Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China;School of Pharmaceutical and Chemical Engineering,Taizhou University,Taizhou 318000,China;Department of Chemistry,Zhejiang Sci-Tech University,Hangzhou 310018,China)

机构地区：[1]中国科学院上海有机化学研究所,中国科学院有机氟化学重点实验室,上海200032 [2]台州学院医药化工学院,台州318000 [3]浙江理工大学化学系,杭州310018

出　　处：《中国科学：化学》2023年第3期375-387,共13页SCIENTIA SINICA Chimica

基　　金：国家重点研发计划(编号:2021YFF0701700);国家自然科学基金(编号:22271299,21632009)资助项目。

摘　　要：与三氟甲基类似,二氟甲基对于药物开发非常重要,而(二氟甲基)三甲基硅烷试剂(Me3SiCF_(2)H,经常被简写为TMSCF_(2)H)是最常用的二氟甲基化试剂之一.TMSCF_(2)H试剂参与的二氟甲基化反应曾长时间不受重视直到2011年之后才不断被报道.本文综述了TMSCF_(2)H试剂的制备方法,并根据不同反应类型的分类(亲核加成、亲核取代、金属参与的交叉偶联反应、C–H键官能团化等),综述了TMSCF_(2)H参与的各类二氟甲基化反应的研究进展.Compared with(trifluoromethyl)trimethylsilane(TMSCF3),the analogous(difluoromethyl)trimethylsilane(TMSCF_(2)H)was considered as a sluggish difluoromethylation reagent before 2011 because of the reported difficulty in breaking the C–Si bond in 1995.However,in 2011,a breakthrough was reported and(difluoromethyl)trimethylsilane(TMSCF_(2)H),initiated by a suitable Lewis base,was able to undergo difluoromethylation under mild conditions.In the following more than ten years,organic reactions involving TMSCF_(2)H have been continuously reported.In this paper,we review the preparation of TMSCF_(2)H and the progress of its applications in organic synthesis,such as nucleophilic addition,nucleophilic substitution,metal-mediated cross-coupling reactions,and C–H functionalization,among others.

关 键 词：(二氟甲基)三甲基硅烷 二氟甲基化 亲核加成 亲核取代 交叉偶联反应 C–H键活化 

分 类 号：TQ460.1[化学工程—制药化工] O623.2[理学—有机化学]