A new cooperative nickel reductive catalysis and N,N-dimethylformamide-mediated strategy for umpolung C–S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides to produce alkyl...A new cooperative nickel reductive catalysis and N,N-dimethylformamide-mediated strategy for umpolung C–S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides to produce alkyl aryl thioethers is described. This reaction features excellent selectivity, wide functionality tolerance, broad substrate scope, and facile late-stage modification of biologically relevant molecules.Mechanistic studies recognize initial generation of an amidyl radical anion via thermoinduced reduction of DMF with Sn, followed by umpolung reduction and single electron transfer of the nucleophilic sulfonyl moiety to form a sulphydryl radical and engage the Ni^(0)/Ni^(Ⅰ)/Ni^(Ⅲ)/Ni^(I) catalytic cycle.展开更多
The copper-mediated trifluoromethylation of terminal alkynes with S-（trifluoromethyl）diarylsulfonium salt has been carefully investigated. The reactions proceeded smoothly to afford trifluoromethylated acetylenes in...The copper-mediated trifluoromethylation of terminal alkynes with S-（trifluoromethyl）diarylsulfonium salt has been carefully investigated. The reactions proceeded smoothly to afford trifluoromethylated acetylenes in moderate to good yields. This approach is a convenient method to synthesize a variety of functional trifluoromethylated acetylenes.展开更多
基金the National Natural Science Foundation of China(No.22271245)the Jiangxi Province Science and Technology Project(Nos.20212AEI91002 and 20202ACBL213002)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(No.2021ZD01)for financial support.
文摘A new cooperative nickel reductive catalysis and N,N-dimethylformamide-mediated strategy for umpolung C–S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides to produce alkyl aryl thioethers is described. This reaction features excellent selectivity, wide functionality tolerance, broad substrate scope, and facile late-stage modification of biologically relevant molecules.Mechanistic studies recognize initial generation of an amidyl radical anion via thermoinduced reduction of DMF with Sn, followed by umpolung reduction and single electron transfer of the nucleophilic sulfonyl moiety to form a sulphydryl radical and engage the Ni^(0)/Ni^(Ⅰ)/Ni^(Ⅲ)/Ni^(I) catalytic cycle.
基金Acknowledgement We thank the National Natural Science Foundation of China （Nos. 21032006, 21172240）, the 973 Program of China （No. 2012CBA01200）, the Chinese Academy of Sciences for financial support.
文摘The copper-mediated trifluoromethylation of terminal alkynes with S-（trifluoromethyl）diarylsulfonium salt has been carefully investigated. The reactions proceeded smoothly to afford trifluoromethylated acetylenes in moderate to good yields. This approach is a convenient method to synthesize a variety of functional trifluoromethylated acetylenes.
