Well‐Defined and Robust Rhodium Catalysts for the Hydroacylation of Terminal and Internal Alkenes

A Rh-catalyst system based on the asymmetric ligand tBu2PCH2P(o-C6H4OMe)2 is reported that allows for the hydroacylation of challenging internal alkenes with β-substituted aldehydes. Mechanistic studies point to the stabilizing role of both excess alkene and the OMe-group.