Mechanistic studies on the Pd-catalyzed vinylation of aryl halides with vinylalkoxysilanes in water: The effect of the solvent and NaOH promoter

The mechanism of the Pd-catalyzed vinylation of aryl halides with vinylalkoxysilanes in water has been studied using different catalytic precursors. The NaOH promoter converts the initial vinylalkoxysilane into a highly reactive water-soluble vinylsilanolate species. Similarly, deuterium-labeling experiments have shown that, irrespective of the catalytic precursor used, vinylation occurs exclusively at the CH vinylic functionality via a Heck reaction and not at the C-Si bond via a Hiyama cross-coupling. The involvement of a Heck mechanism is interpreted in terms of the reduced nucleophilicity of the base in water, which disfavors the transmetalation step. The Heck product (β-silylvinylarene) undergoes partial desilylation, with formation of a vinylarene, by three different routes: (a) hydrolytic desilylation by the aqueous solvent (only at high temperature); (b) transmetalation of the silyl olefin on the PdH Heck intermediate followed by reductive elimination of vinylarene; (c) reinsertion of the silyl olefin into the PdH bond of the Heck intermediate followed by β-Si syn-elimination. Both the Hiyama and Heck catalytic cycles and desilylation mechanisms b and c have been computationally evaluated for the [Pd(en)Cl2] precursor in water as solvent. The calculated Gibbs energy barriers support the reinsertion route proposed on the basis of the experimental results. © 2013 American Chemical Society.