Ligand-Controlled Palladium-Catalyzed Regiodivergent Defluorinative Allylation of gem-Difluorocyclopropanes viaσ-Bond Activation  

作　　者：Lei Wu Minyan Wang Yong Liang Zhuangzhi Shi 

机构地区：[1]State Key Laboratory of Coordination Chemistry,School of Chemistry and Chemical Engineering,Nanjing University,Nanjing,Jiangsu,210093 China [2]School of Chemistry and Chemical Engineering,Henan Normal University,Xinxiang,Henan,453007 China

出　　处：《Chinese Journal of Chemistry》2022年第19期2345-2355,共11页中国化学（英文版）

基　　金：the National Natural Science Foundation of China(Grants 22025104,21972064 and 21901111);the Fundamental Research Funds for the Central Universities for their financial support(Grant 020514380254);The project was also supported by Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University.

摘　　要：Monofluoroalkenes are important and versatile privileged components in pharmacologically relevant molecules.Here,we report a method for the selective construction of these compounds in a diversity-oriented fashion through regiodivergent cross-coupling of gem-difluorocyclopropanes with allylboronates by employing a palladium catalyst with two different ligands,in which gem-difluorocyclopropanes were used as allyl electrophiles by C—C and C—F bond activation.In the presence of 2-biphenylyl(diphenyl)phosphine as ligand,the linear-selective allyl–allyl bond formation is highly obtained,while utilizing the sterically hindered BrettPhos(dicyclohexyl[3,6-dimethoxy-2',4',6'-tris(1-methylethyl)[1,1'-biphenyl]-2-yl]phosphine)as the ligand favors the generation of the branched-selective product.Experimental and computational studies investigated the key steps of the cross-coupling reactions,revealing the origin of the ligand-controlled regiodivergence.

关 键 词：ALLYLATION C-C activation CROSS-COUPLING gem-Difluorocyclopropanes DEFLUORINATION 

分 类 号：O62[理学—有机化学]