Nickel‐catalyzed umpolung C[sbnd]S radical reductive cross coupling of S‐(trifluoromethyl)arylsulfonothioates with alkyl halides

Abstract

A new cooperative nickel reductive catalysis and N,N-dimethylformamide-mediated strategy for umpolung CS 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 Ni0/NiI/NiIII/NiI catalytic cycle.