镍催化下3,3,3-三氟丙烯与芳基锌试剂的区域选择性偶联反应  

Nickel-Catalyzed Regioselective Coupling Reaction of 3,3,3-Trifluoropropene with Arylzinc Reagents

作　　者：程然 徐畅 张新刚[1] Cheng Ran;Xu Chang;Zhang Xingang(Key Laboratory of Organofluorine Chemistry,Center for Excellence in Molecular Synthesis,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,University of Chinese Academy of Sciences,Shanghai 200032)

机构地区：[1]中国科学院上海有机化学研究所分子合成卓越中心,中国科学院有机氟化学重点实验室,中国科学院大学,上海200032

出　　处：《有机化学》2020年第10期3307-3313,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.21931013,21672238,21421002);中国科学院先导专项(No.XDB20000000)资助项目。

摘　　要：3,3,3-三氟丙烯是一类廉价易得的含氟工业原料,在工业生产上有着重要的应用,其巨大的应用潜力仍值得深入研究,因此探索新型反应路径对三氟丙烯的高效转化具有重要意义.报道了一种镍催化下芳基锌试剂与3,3,3-三氟丙烯高区域选择性偶联反应.通过反应溶剂的调控可以选择性生成偏氟烯烃和Heck型三氟丙烯衍生物,具有反应条件温和以及底物普适性好等特点,为3,3,3-三氟丙烯的高效转化提供了一种新的路径.3,3,3-Trifluoropropene(TFP)is an inexpensive and bulk industrial material and has important applications in the production of fluorinated polymers,refrigerant and so on.The use of TFP as a fluorine source enables access to a variety of fluorinated compounds.To date,important progress has been made in the transformations of TFP,however,most of the developed methods focused on the functionalization of carbon-carbon double bond of TFP.The controllable formation of fluorinated products via regio-selective functionalization of TFP received less attention.Herein,a nickel-catalyzed regioselective coupling of TFP with arylzinc reagents is described.By fine-tuning the reaction solvent,two different types of fluorinated products,gem-difluoroalkenes and Heck-type aryl-substituted TFPs,were obtained.The use of dioxane as the solvent led to a series of gem-difluoroalkenes in moderate to good yields with high regio-selectivity and functional group tolerance under mild reaction conditions.While,switching solvent from dioxane to N,N-dimethylformamide(DMF),the Heck-type aryl-substituted TFPs were obtained.This regioselective coupling provides an efficient route for applications of TFP in organic synthesis.

关 键 词：3 3 3-三氟丙烯 镍催化 芳基锌试剂 交叉偶联 

分 类 号：O621.251[理学—有机化学]