A general method for the synthesis of bench-stable bis(difluoromethyl)pentacoordinate phosphoranes has been developed.The reaction is rapid,operationally simple,and easily scalable.The pentacoordinate phosphoranes can...A general method for the synthesis of bench-stable bis(difluoromethyl)pentacoordinate phosphoranes has been developed.The reaction is rapid,operationally simple,and easily scalable.The pentacoordinate phosphoranes can generate both difluoromethyl radical(·CF_(2)H)and difluorocarbene(:CF_(2))intermediates.Thus,a variety of fluoroalkylation transformations havebeen achieved by·CF_(2)H,such asoxidativedifluoromethylation of electron-deficient heterocycles,nickel/photoredox dual-catalyzed difluoromethylation of aryl bromides,and photoredox difluoromethylation of alkenes,or by:CF_(2),such as gem-difluorocyclopropanation of alkenes,base-promoted difluoromethylation of heteroatom nucleophiles,Pd-catalyzed difluoromethylation of arylboronic acids,and Cu-mediated trifluoromethylation of aryl iodides(via:CF_(2) and recombined CF_(3)-).These fluoroalkylation methods have been successfully applied to late-stage fluoroalkylation of drugs and drug-like molecules.展开更多
A copper-mediated deuterotrifluoromethylation of α-diazo esters under the promotion of deuterium oxide （D20） has been developed for the synthesis of deuterium-labeled trifluoromethyl compounds. This deuterotrifluor...A copper-mediated deuterotrifluoromethylation of α-diazo esters under the promotion of deuterium oxide （D20） has been developed for the synthesis of deuterium-labeled trifluoromethyl compounds. This deuterotrifluoromethyl- ation reaction is of broad scope and can afford the deuterated products with higher than 99% isotopic purity. More- over, the results of this investigation also provide some experimental evidences to support our previously proposed trifluoromethylation mechanism.展开更多
A practical method for the synthesis of allylic thioacyanates from allylic alcohols was disclosed employing K_(2)S_(2)O_(8) as the oxidant and NH_(4)SCN as the thiocyanate source.Without introducing a leaving group in...A practical method for the synthesis of allylic thioacyanates from allylic alcohols was disclosed employing K_(2)S_(2)O_(8) as the oxidant and NH_(4)SCN as the thiocyanate source.Without introducing a leaving group in advance,a series of disubstituted and monosubstituted allylic thiocyanate compounds were obtained in moderate to good yields.This transition metal-free method features mild reaction conditions,broad sub-strate scope and operational simplicity.The potential application of this method was demonstrated by some derivatization reactions of the product and mechanistic investigation indicated that a radical process is involved.展开更多
An efficient trifluoromethylation reaction of vinyldiazoacetates under mild reaction conditions was depicted.Pre-generated CuCF_(3) was used as a trifluoromethylation reagent and water acted as both a promoter and pro...An efficient trifluoromethylation reaction of vinyldiazoacetates under mild reaction conditions was depicted.Pre-generated CuCF_(3) was used as a trifluoromethylation reagent and water acted as both a promoter and proton source.The reaction is compatible with a broad scope of functional groups and easy to scale-up.The wide functional group tolerance of the reaction enables further synthetic manipulation of the products.展开更多
基金supported by National Natural Science Foundation of China(grant no.21901196)the Natural Science Basic Research Plan in Shaanxi Province of China(grant nos.2020JQ-016 and 2021GXLH-Z-096)+1 种基金the Fundamental Research Funds for the Central Universities(grant no.xhj032021007-01)Xi’an Jiaotong University(grant no.71211920000001).
文摘A general method for the synthesis of bench-stable bis(difluoromethyl)pentacoordinate phosphoranes has been developed.The reaction is rapid,operationally simple,and easily scalable.The pentacoordinate phosphoranes can generate both difluoromethyl radical(·CF_(2)H)and difluorocarbene(:CF_(2))intermediates.Thus,a variety of fluoroalkylation transformations havebeen achieved by·CF_(2)H,such asoxidativedifluoromethylation of electron-deficient heterocycles,nickel/photoredox dual-catalyzed difluoromethylation of aryl bromides,and photoredox difluoromethylation of alkenes,or by:CF_(2),such as gem-difluorocyclopropanation of alkenes,base-promoted difluoromethylation of heteroatom nucleophiles,Pd-catalyzed difluoromethylation of arylboronic acids,and Cu-mediated trifluoromethylation of aryl iodides(via:CF_(2) and recombined CF_(3)-).These fluoroalkylation methods have been successfully applied to late-stage fluoroalkylation of drugs and drug-like molecules.
文摘A copper-mediated deuterotrifluoromethylation of α-diazo esters under the promotion of deuterium oxide （D20） has been developed for the synthesis of deuterium-labeled trifluoromethyl compounds. This deuterotrifluoromethyl- ation reaction is of broad scope and can afford the deuterated products with higher than 99% isotopic purity. More- over, the results of this investigation also provide some experimental evidences to support our previously proposed trifluoromethylation mechanism.
基金L.Liu thanks the National Natural Science Foundation of China(21901199)Xi’an Jiaotong University(7121192002)for financial support.
文摘A practical method for the synthesis of allylic thioacyanates from allylic alcohols was disclosed employing K_(2)S_(2)O_(8) as the oxidant and NH_(4)SCN as the thiocyanate source.Without introducing a leaving group in advance,a series of disubstituted and monosubstituted allylic thiocyanate compounds were obtained in moderate to good yields.This transition metal-free method features mild reaction conditions,broad sub-strate scope and operational simplicity.The potential application of this method was demonstrated by some derivatization reactions of the product and mechanistic investigation indicated that a radical process is involved.
基金the National Natural Science Foundation of China(21901196)the Natural Science Basic Research Plan in Shaanxi Province of China(2020JQ-016)Xi’an Jiaotong University(71211920000001)for financial support.
文摘An efficient trifluoromethylation reaction of vinyldiazoacetates under mild reaction conditions was depicted.Pre-generated CuCF_(3) was used as a trifluoromethylation reagent and water acted as both a promoter and proton source.The reaction is compatible with a broad scope of functional groups and easy to scale-up.The wide functional group tolerance of the reaction enables further synthetic manipulation of the products.
