Manganese-Catalyzed Asymmetric Transfer Hydrogenation of Polarized Olefins via a Collaborative Hydrogen Transfer...

Asymmetric (transfer) hydrogenation of olefins is an important route to chiral molecules used in pharmaceuticals, agrochemicals, and fine chemicals. Although this transformation is well established with ruthenium-, rhodium-, and iridium-based catalysts, analogous reactions catalyzed by earth-abundant metals remain limited, particularly for acyclic olefins. Here we report a manganese catalytic system that enables highly enantioselective reduction of both cyclic and acyclic olefins, delivering diverse chiral products in up to 99% yield and >99% ee. Density functional theory (DFT) studies indicate that the reaction proceeds predominantly through a concerted hydrogen-transfer pathway involving a six-membered transition state. These results expand the scope of manganese-catalyzed asymmetric olefin transfer hydrogenation and provide mechanistic insight into hydrogen transfer by base-metal catalysts.