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Abstract Metallaphotoredox catalysis has evolved into an enabling platform to construct C(sp 3 )‐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(sp 2 )–C(sp 3 ) 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.
Lipp et al. (Fri,) studied this question.