Ni-Catalyzed Reductive Liebeskind–Srogl Alkylation of Heterocycles

[Image: see text] Herein we present a Ni-catalyzed alkylation of C–SMe with alkyl bromides for the decoration of heterocyclic frameworks. The protocol, reminiscent to the Liebeskind–Srogl coupling, makes use of simple C(sp(2))–SMe to be engaged in a reductive coupling. The reaction is suitable for a preponderance of highly valuable heterocyclic motifs. In addition to cyclic bromides, noncyclic alkyl bromides are well accommodated with exquisite levels of retention over isomerization. The protocol is scalable and permits orthogonal couplings in the presence of other functionalization handles.