Directed, nickel-catalyzed 1,2-alkylsulfenylation of alkenyl carbonyl compounds.

We report a regioselective, nickel-catalyzed syn -1,2-carbosulfenylation of non-conjugated alkenyl carbonyl compounds with alkyl/arylzinc nucleophiles and tailored N-S electrophiles. This method allows the simultaneous installation of a variety of C(sp 3 ) and S(Ar) (or Se(Ar)) groups onto unactivated alkenes, which complements previously developed 1,2-carbosulfenylation methodology in which only C(sp 2 ) nucleophiles are compatible. A bidentate directing auxiliary controls regioselectivity, promotes high syn -stereoselectivity with a variety of E - and Z -internal alkenes, and enables the use of an array of electrophilic sulfenyl (and seleno) electrophiles. Among compatible electrophiles, those with N -alkyl-benzamide leaving groups were found to be especially effective, as determined through comprehensive structure-reactivity mapping.