Rhodium‐Catalyzed Asymmetric Synthesis of β‐Branched Amides

A general asymmetric route for the one‐step synthesis of chiral β‐branched amides is reported through the highly enantioselective isomerization of allylamines, followed by enamine exchange, and subsequent oxidation. The enamine exchange allows for a rapid and modular synthesis of various amides, including challenging β‐diaryl and β‐cyclic. A domino process: A RhI/chiral BINAP catalysis is reported for the one‐step modular synthesis of chiral β‐branched amides with various amine nucleophiles. β‐dialkyl, β‐diaryl, and β‐alkylaryl stereocenters are established under identical conditions with excellent enantio‐ and diastereoselectivity in a ligand‐controlled manner.