Cobalt‐Catalyzed Asymmetric Construction of Boron Stereocenters With C–N Axial Chirality

Abstract

ABSTRACT The efficient construction of boron stereogenic centers alongside axial chirality remains a significant synthetic challenge, particularly under one‐pot conditions. Herein, we report a cobalt/Salox‐catalyzed enantioselective annulation strategy that enables the simultaneous formation of B‐stereogenic frameworks and a C─N chiral axis via C─H and N─H annulation of arylamides with dialkynylborons. This protocol achieves asymmetric desymmetrization at boron along with effective diastereocontrol on the C─N axis under mild conditions. A wide range of aryl amides and alkynes are well tolerated, delivering structurally diverse products in good yields with consistently high diastereo‐ and enantioselectivities. Mechanistic studies, including control experiments and isotope labelling, provide insight into the reaction pathway and the origin of stereocontrol. The resulting chiral boron‐containing compounds exhibit notable fluorescence, and their photophysical properties suggest potential utility in optoelectronic applications.