Selective nickel-catalyzed disulfuration of alkyl halides with di/trithiosulfonates

Abstract

The utilization of electrophilic di/trithiosulfonates in nickel-catalyzed reductive coupling for selective conversion has rarely been investigated, and the activation modes are also unclear and challenging. Here we report the selective reductive disulfuration of a wide variety of alkyl halides using di/trithiosulfonate reagents enabled by a simple dual-role nickel catalyst and reductant. This excellent selectivity can be achieved through ligand regulation. Mechanistic studies suggest that the key aspect of this reaction could be the employment of the differential reduction potential of PhSO₂(S)_nR (n = 2, 3; R = alkyl) favoring reduction to alkyl tetrasulfide species for selective thiolation in a controllable fashion. This strategy might provide new opportunities and mechanistic insights for nickel-catalyzed coupling of di/trithiosulfonate reagents with various alkyl halides to access valuable disulfide products with good functional group compatibility.