Manganese‐Catalyzed Asymmetric Transfer Hydrogenation of Polarized Olefins via a Collaborative Hydrogen Transfer Process

ABSTRACT 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.