Switching Mechanistic Pathways by Micellar Catalysis: A Highly Selective Rhodium Catalyst for the Hydroaminomethylation of Olefins with Anilines in Water

Hydroaminomethylation (HAM) is one of the most promising atom-economic processes for the production of secondary amines, which so far remains extremely challenging with anilines as substrates. Herein, we report the use of combined micellar and microwave catalysis for the HAM of olefins with anilines in water as the reaction medium that allows for the synthesis of secondary anilines in good yields and with high regioselectivities. For the micellar rhodium/xantphos catalyst system, mechanistic investigations suggest a pathway different to the commonly observed mechanisms with homogeneous catalysts for the reported HAM reaction, involving a carbonylation initiated by a C-H activation rather than classical hydroformylation steps. © 2023 American Chemical Society.