Enantioselective Hydroaminomethylation of Olefins Enabled by Rh/Brønsted Acid Relay Catalysis.

Herein, by employing a rhodium catalyst with a commercial ligand and a phosphoric acid catalyst, highly chemo-, regio-, and enantioselective hydroaminomethylation of olefins is realized through a relay catalytic hydroformylation/dynamic kinetic reductive amination process. The method features mild conditions (1 bar of syngas, room temperature in most cases), high yields (up to 99%), and high enantioselectivities (up to >99.5:0.5 er). Besides styrenes, acrylamides also provided the products with high yields and enantioselectivities. Aliphatic alkenes and vinyl esters are also applicable for the current method, albeit lower yields and enantioselectivities were obtained.