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 thr...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.展开更多
The atom-economical C-F insertion chemistry is emerged as a promising technology for the synthesis of various fluorinated scaffolds,which have wide applications both in the academic and the industrial com-munities.The...The atom-economical C-F insertion chemistry is emerged as a promising technology for the synthesis of various fluorinated scaffolds,which have wide applications both in the academic and the industrial com-munities.The past three years have witnessed rapid developments in this field.This highlight provides an overview on the evolution according to the fluorinating agents used.展开更多
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.
文摘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.
基金The Tertiary Education Scientific Research Project of Guangzhou Municipal Education Bureau(No.202235305)is gratefully acnowledged for financial support.
文摘The atom-economical C-F insertion chemistry is emerged as a promising technology for the synthesis of various fluorinated scaffolds,which have wide applications both in the academic and the industrial com-munities.The past three years have witnessed rapid developments in this field.This highlight provides an overview on the evolution according to the fluorinating agents used.
