Novel diphosphine-modified palladium catalysts for oxidative carbonylation of styrene to methyl cinnamate †

Palladium–dppb–borate‐catalyzed regioselective synthesis of cinnamate esters by alkoxycarbonylation of phenylacetylene

“…It could be explained by the fact that acetonitrile is acting as both solvent and co-ligand. [3,42] In cationic complexes the fourth coordination position could be occupied by acetonitrile, which probably plays an active role in the migratory insertion. [43] It is apparent that the nucleophilic character of the co-ligand may remarkably affect the rate of conversion of [Pd(P-P)H] + into [Pd(P-P)OMe] + and hence promote the products of carbonylation whose formation required a Pd-H bond.…”

“…[3,7 -9] The disadvantages of these methods are a large excess of oxidant (copper (II) salt), [10] and lack of selectivity due to many side products. [3] Alkoxycarbonylation of phenylacetylene with alcohols normally gives trans-and gem-α,β-unsaturated esters [1 and 2; Eq. (1)].…”

“…[1,2] Cinnamic acid and its esters are important intermediates for the production of pharmaceuticals, fragrances, light-sensitive and electrically conductive materials and agrochemicals. [3] Cinnamate esters are made conventionally through Claisen condensation from benzaldehyde and alkylacetate in the presence of sodium alkoxide [4] or by esterification of cinnamic acid, [5] or by using palladium acetate-tertiary phosphine as a catalyst in the reaction of phenyl bromide and an alkyl acrylate. [6] Many publications and patents disclose oxidative carbonylation of olefins to α,β-unsaturated esters by reacting an olefin with carbon monoxide, oxygen, and an alcohol in the presence of palladium and copper salts.…”

CO/C‐H as an Acylating Reagent: A Palladium‐Catalyzed Aerobic Oxidative Carbonylative Esterification of Alcohols

“…[6e,8,11] Initially, an alkoxy palladium intermediate B is generated from the reaction between 1 and the Pd II species A through an alcoholysis step. [6e,8,11] Initially, an alkoxy palladium intermediate B is generated from the reaction between 1 and the Pd II species A through an alcoholysis step.…”

Palladium‐Catalyzed Carbonylation Reactions of Alkenes and Alkynes

“…[19] Alkoxycarbonylation reactions are more popular for academic investigations because of the convenient product purification compared to hydroxycarbonylations. Analogous bisalkoxycarbony-lation of the starting material provides a convenient route to diesters.…”