Regioselective 1,2-Carbosulfenylation of Unactivated Alkenes via Directed Nickel Catalysis

Abstract

A bidentate directing group-assisted Ni-catalyzed three component 1,2-carbosulfenylation of unactivated alkenes with aryl/alkenyloronic 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 α-position furnish α,γ-dibranched thiolamines with high diastereoselectivity and enantioselectivity that would otherwise be difficult to synthesize. The generality and scability could make this method attractive for preparing complex organosulfur compounds.

Recent developments on 1,2-difunctionalization and hydrofunctionalization of unactivated alkenes and alkynes involving C–S bond formation

“…Besides sulfonamide sulfenylating agents, the Wang group 73 found that simple aryl disulfides (250, Scheme 42) were also competent to oxidize Ni(I) (254) to the sulfenyl Ni(III) intermediate ( 255) and furnish the 1,2-arylsulfenylation products (251) chemo-and regioselectively from unactivated alkenes (248) and arylboronic acids (249). In this process, the assistance of the intramolecular bidentate coordination of PA auxiliary ( picolinamide) was proposed to stabilize the active nickel intermediates.…”

Catalytic Arylalkylation of Alkenyl Amines at Remote Sites via Directed Nickel Catalysis

“…Among the various synthetic methods, metal‐catalyzed difunctionalization of alkenyl amines has emerged as a powerful strategy for the efficient construction of value‐added complex alkylamines from easily accessible starting materials. [ 3‐11 ] Considering that the structure of alkyl groups appended to the nitrogen atom would influence the physical properties and control the biological interactions, [ 12‐13 ] difunctionalization of alkenyl amines at various sites would be highly desirable to prepare new aliphatic amines, especially those that are difficult to access using traditional methods.…”