Manganese‐Catalyzed Hydrofunctionalization of Alkenes

The manganese‐catalyzed hydrosilylation and hydroboration of alkenes has been developed using a single manganese(II) precatalyst and reaction protocol. Both reactions proceed with excellent control of regioselectivity and in high yields across a variety of sterically and electronically differentiated substrates (25 examples). Alkoxide activation, using NaOtBu, was key to precatalyst activation and reactivity. Catalysis was achieved across various functional groups and on gram‐scale for both the developed methodologies with catalysts loadings as low as 0.5 mol %. Mn platform: A single catalyst/activator platform is reported for the manganese‐catalyzed hydrosilylation and hydroboration of alkenes. The systems hinge on NaOtBu operating as an activator, and the reaction uses bench‐stable catalysts and reagents. Both reactions proceed with high regioselectivity (up to >99:1) and high yields (up to >95 %).