Carbonylation of Olefins under Mild Temperature Conditions in the Presence of Palladium Complexes

Abstract

During a search for catalysts that allow carbonylation reactions on olefins to proceed below 100 °C, complex palladium(II) compounds having the formula LmPdXn were found to be catalytically active. L denotes a ligand such as a phosphine, nitrile, amine, or olefin, X is an acid residue, and m+n is 3 or 4. The catalysts permit the carbonylation of heat‐sensitive compounds, as well as selective carbonylation of polyunsaturated olefins. The new process can also be carried out on the industrial scale, as is shown by the carbonylation of cyclododecatriene

Catalytic Markovnikov and anti‐Markovnikov Functionalization of Alkenes and Alkynes: Recent Developments and Trends

“…Clearly, the special thermodynamic stability of the transition-metal benzyl complex is the main factor that governs the regioselectivity of this functionalization process. For instance, PdCl 2 [72] and [PdCl 2 (PPh 3 ) 2 ] [73] along with 10 % HCl in ethanol catalyze the carbonylation of styrene to ethyl-2-phenyl propionate with 95 % yields. Hydrocarboxylation and hydroesterification (alkoxycarbonylation) of 4-methylstyrene with PdCl 2 /CuCl 2 / HCl as the catalyst system in the presence of PPh 3 as a ligand, gave the corresponding branched aryl propionic acid and ester [74] in 93 % regioselectivity.…”

Polymer precursors from catalytic reactions of natural oils

“…The first palladium catalysts developed in the 1960's were shown to be active at much lower temperature (about 100℃) than cobalt catalysts. [89][90][91][92][93] The introduction of phosphine ligands into the palladium system by Drent and co-workers in the 1980's led to a major progress in the field of alkoxycarbonylation. 94 The reader will now have an overview of a diphosphine ligand that shows outstanding activities towards the alkoxycarbonylation reaction.…”

Carbonylation of Alkynes, Alkenes and Alcohols using Metal Complex Catalysts

“…However, with the proper choice of solvents using the same catalyst system, linear carboxylic acids and esters with high yields were reported by Knifton [15] which gave the linear isomer predominantly (65-85%) under comparatively lower CO pressures (20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30). Other low temperature processes were reported by Reis and co-workers [16] (operating at high pressures $30-70 MPa, 313 K), and Tsuji et al [17,18] (in an alcoholic solution of HCl in the presence of PdCl 2 ) for carbonylation of olefins. The use of group IVB metal halide promoters such as SnCl 2 , GeCl 2 and PbCl 2 for carbonylation of a-olefins showed a good linear ester selectivity (Knifton [19]) at mild conditions (353 K, 30 MPa).…”