Asymmetric Rh-Catalyzed Synthesis of Dihydronicotinamides

We report a rhodium-catalyzed enantioselective dearomatization of nicotinamide-derived pyridinium salts to access primary, secondary, and tertiary dihydropyridine carboxamides with high regio- and enantioselectivity (up to 99% ee). Employing arylboronic acid pinacol esters and Rh/(<i>R</i>)-Xyl-BINAP, the reaction tolerates diverse functional groups, enabling a versatile approach for synthesizing chiral azaheterocycles with pharmaceutical relevance.