Manganese-Catalyzed Asymmetric Hydrogenation of Electron-Deficient Olefins

Earth-abundant manganese-catalyzed asymmetric hydrogenation has emerged as a sustainable alternative to noble metal systems, achieving remarkable success in the reduction of polar C═O, C═N, and heteroaromatic substrates. However, because the polar and nucleophilic Mn-H species are inherently mismatched with nonpolar C═C bonds, asymmetric hydrogenation of C═C bonds with manganese catalysts remains a challenging and unexplored area. Herein, we disclose the first manganese-catalyzed asymmetric hydrogenation of electron-deficient polarized olefins enabled by an efficient metal-ligand cooperation process utilizing 2-hydroxypyridine-oxazoline ligands. This strategy delivers a broad range of substrates with up to 99% yield with 98% enantiomeric excess. Moreover, this catalytic system enables the hydrogenation kinetic resolution of racemic 4-aryl-quinolin-2-ones, affording axial-chiral recovered substrates with selectivity factor up to 178. These results pave up a new platform for manganese-catalyzed asymmetric hydrogenation, expanding the scope of earth-abundant metal catalysis in enantioselective synthesis.