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.

Automated summary

We report a regioselective, nickel-catalyzed carbosulfenylation reaction that introduces both C(sp(3)) and S(Ar)(or Se(Ar)) groups onto non-conjugated alkenyl carbonyl compounds. This reaction is compatible with alkyl/arylzinc nucleophiles and tailored N-S electrophiles, and is complementary to the previously developed 1,2-carbosulfenylation methodology that only allows C(sp(2)) nucleophiles.