Palladium-catalyzed oxidative carbonylation of N-aryl enamino esters with CO and alcohols: synthesis of N-aryl aminomethylenemalonates.

A novel palladium-catalyzed regioselective oxidative carbonylation of tri-substituted alkenes with CO and alcohols for the synthesis of α,β-unsaturated esters has been developed. Experimental studies and DFT calculations suggested that the reaction proceeded through alkoxylation of the palladium(ii) catalyst, CO and C[double bond, length as m-dash]C double bond migratory insertion, β-(N)H elimination and tautomerization cascade steps. The reaction tolerates a wide range of groups and produces valuable aminomethylenemalonates in high yields.