Beyond Carbon: Enantioselective and Enantiospecific Reactions with Catalytically Generated Boryl- and Silylcopper Intermediates

[Image: see text] Catalytic asymmetric C–C bond formation with alkylcopper intermediates as carbon nucleophiles is now textbook chemistry. Related chemistry with boron and silicon nucleophiles where the boryl- and accordingly silylcopper intermediates are catalytically regenerated from bench-stable pronucleophiles had been underdeveloped for years or did not even exist until recently. Over the past decade, asymmetric copper catalysis employing those main-group elements as nucleophiles rapidly transformed into a huge field in its own right with an impressive breadth of enantioselective C–B and C–Si bond-forming reactions, respectively. Its current state of the art does not have to shy away from comparison with that of boron’s and silicon’s common neighbor in the periodic table, carbon. This Outlook is not meant to be a detailed summary of those manifold advances. It rather aims at providing a brief conceptual summary of what forms the basis of the latest exciting progress, especially in the area of three-component reactions and cross-coupling reactions.