溴二氟甲基三甲基硅烷的合成及其在有机合成中的应用  

Synthesis of(Bromodifluoromethyl)trimethylsilane and Its Applications in Organic Synthesis

作　　者：涂志 余金生 周剑 Tu Zhi;Yu Jinsheng;Zhou Jiana(Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development,Shanghai Key Laboratory of Green Chemistry and Chemical Processes,School of Chemistry and Molecular Engineering,East China Normal University,Shanghai 200062;State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032;Key Laboratory of Tropical Medicinal Resource Chemistry of Ministry of Education,Hainan Normal University,Haikou 571127)

机构地区：[1]华东师范大学化学与分子工程学院、上海分子治疗与新药创制工程技术研究中心、上海市绿色化学与化工过程绿色化重点实验室,上海200062 [2]中国科学院上海有机化学研究所金属有机化学国家重点实验室,上海200032 [3]海南师范大学热带药用资源化学教育部重点实验室,海口571127

出　　处：《有机化学》2023年第10期3491-3507,共17页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.22171087,21971067);上海市教育委员会科研创新计划(No.2023ZKZD37);上海市科技创新行动计划(Nos.21N41900500,20JC1416900)资助项目。

摘　　要：溴二氟甲基三甲基硅烷(TMSCF_(2)Br)自2011年首次被作为二氟卡宾前体报道以来,已发展成为一种重要的二氟甲(烷)基化试剂,并在有机合成中得到了广泛应用.在简要介绍TMSCF_(2)Br合成方法的基础上,重点阐述了利用TMSCF_(2)Br作为二氟卡宾前体或三甲基硅基二氟甲基自由基前体实现不同底物的系列二氟甲基或氟烷基化反应的研究进展.藉此对TMSCF2Br在有机合成反应的活化方式和机理及其应用优势与不足等进行分析讨论,为从事有机合成和有机氟化学相关的科研人员提供一些参考与启发.Bromodifluoromethyl trimethylsilane(TMSCF_(2)Br)has proved to be an important difluoromethyl(alkyl)ation reagent that is widely applied in organic synthesis over the past decade,since it was used as a difluorocarbene precursor in 2011.This review aims to provide a briefly summary for the synthesis of TMSCF_(2)Br,and to introduce the recent advances in the applications of TMSCF_(2)Br as a difluorocarbene or trimethylsilyldifluoromethyl radical precursor for developing various difluoromethyl(alkyl)ations of different kinds of substrates.Meanwhile,the activation ways of TMSCF_(2)Br and the possible mechanism,as well as its advantages and disadvantages in each kind of reactions are detailedly disccussed,which might provide some references and inspiration for researchers engaged in organic synthesis and organic fluorine chemistry.

关 键 词：溴二氟甲基三甲基硅烷 二氟卡宾 三甲基硅基二氟甲基自由基 二氟甲基化 二氟烷基化 

分 类 号：O627.41[理学—有机化学]