Reverse Regioselective Dicarbofunctionalization via Anti-Michael-Type Addition.

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.