Regioselective 1,2-carbosulfenylation of unactivated alkenes via directed nickel catalysis

A bidentate directing group-assisted Ni-catalyzed three component 1,2-carbosulfenylation of unactivated alkenes with aryl/alkenylboronic acids and disulfide electrophiles is reported. The reaction affords the desired products with high levels of chemo- and regioselectivity. A wide range of aryl groups and sulfur moieties can be simultaneously installed in both internal and terminal homoallylic amines with excellent functional group tolerance. Notably, the alkene substrates with a chiral center at the alpha-position furnish alpha,gamma-dibranched thiolamines with high diastereoselectivity and enantioselectivity that would otherwise be difficult to synthesize. The generality and scalability could make this method attractive for preparing complex organosulfur compounds.

Automated summary

In this study, a bidentate directing group-assisted Ni-catalyzed three component 1,2-carbosulfenylation reaction was reported, which allows for the transformation of unactivated alkenes using aryl/alkenylboronic acids and disulfide electrophiles. The reaction showed high levels of chemo- and regioselectivity and could introduce a wide range of aryl groups and sulfur moieties into homoallylic amines. Notably, it also enabled the synthesis of α,gamma-dibranched thiolamines with high diastereoselectivity and enantioselectivity.