Cobalt(II)-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.