Stereoinduction in Metallaphotoredox Catalysis.

Metallaphotoredox catalysis has evolved into an enabling platform to construct C(sp3 )-hybridized centers under remarkably mild reaction conditions. The cultivation of abundant radical precursor feedstocks has significantly increased the scope of transition-metal-catalyzed cross-couplings, especially with respect to C(sp2 )-C(sp3 ) linkages. In recent years, considerable effort has been devoted to understanding the origin of stereoinduction in dual catalytic processes. In this context, Ni- and Cu-catalyzed transformations have played a predominant role exploiting this mode of catalysis. Herein, we provide a critical overview on recent progress in enantioselective bond formations enabled by Ni- and Cu-catalyzed manifolds. Furthermore, selected stereochemical control elements within the realm of diastereoselective transformations are discussed.