Reverse Regioselective Dicarbofunctionalization via <i>Anti</i> ‐Michael‐Type Addition

Abstract

Abstract Vicinal dicarbofunctionalization of α,β‐unsaturated carbonyl compounds is a classical yet versatile method for constructing complex molecular architectures in a single step. However, the regioselectivity is typically governed by the electronic properties of the alkene moiety, leading to the introduction of a nucleophile at the β‐position and an electrophile at the α‐position. Herein, we report a palladium‐catalyzed dicarbofunctionalization of acrylamides via anti ‐Michael‐type addition, achieving reverse regioselectivity relative to traditional approaches. This strategy enables the efficient incorporation of various (hetero)arene nucleophiles at the α‐position and carbon electrophiles, including iodoarenes, vinyl iodides, and iodomethane, at the β‐position to furnish dicarbofunctionalized amides in good yields. Mechanistic investigations suggest that the reaction proceeds through an alkylpalladium intermediate formed via the α‐addition of a nucleophile.