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

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.