Palladium-catalyzed carbonylation reactions of alkenes and alkynes with different nucleophiles have undergone rapid development ever since the seminal work of Reppe back in the 1930s. Nowadays, a plethora of palladium catalysts and various synthetic protocols are available for the synthesis of valuable carboxylic acids and acrylic acids as well as their derivatives. Herein, we summarize the recent catalyst developments and selected organic applications in this area.

Linear carboxylic acid esters from .alpha. olefins. 2. Catalysis by homogeneous palladium complexes

Palladium-Catalyzed Carbonylation Reactions of Alkenes and Alkynes

Organopalladium intermediates in organic synthesis

Hydrido Complexes of Palladium.

The mechanism and kinetics of the solvolysis of complexes of the type [(L-L)Pd(C(O)CH(3))(S)](+)[CF(3)SO(3)](-) (L-L = diphosphine ligand, S = solvent, CO, or donor atom in the ligand backbone) was studied by NMR and UV-vis spectroscopy with the use of the ligands a-j: SPANphos (a), dtbpf (b), Xantphos (c), dippf (d), DPEphos (e), dtbpx (f), dppf (g), dppp (h), calix-6-diphosphite (j). Acetyl palladium complexes containing trans-coordinating ligands that resist cis coordination (SPANphos, dtbpf) showed no methanolysis. Trans complexes that can undergo isomerization to the cis analogue (Xantphos, dippf, DPEphos) showed methanolyis of the acyl group at a moderate rate. The reaction of [trans-(DPEphos)Pd(C(O)CH(3))](+)[CF(3)SO(3)](-) (2e) with methanol shows a large negative entropy of activation. Cis complexes underwent competing decarbonylation and methanolysis with the exception of 2j, [cis-(calix-diphosphite)Pd(C(O)CH(3))(CD(3)OD)](+)[CF(3)SO(3)](-). The calix-6-diphosphite complex showed a large positive entropy of activation. It is concluded that ester elimination from acylpalladium complexes with alcohols requires cis geometry of the acyl group and coordinating alcohol. The reductive elimination of methyl acetate is described as a migratory elimination or a 1,2-shift of the alkoxy group from palladium to the acyl carbon atom. Cis complexes with bulky ligands such as dtbpx undergo an extremely fast methanolysis. An increasing steric bulk of the ligand favors the formation of methyl propanoate relative to the insertion of ethene leading to formation of oligomers or polymers in the catalytic reaction of ethene, carbon monoxide, and methanol.

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Alcoholysis of acylpalladium(II) complexes relevant to the alternating copolymerization of ethene and carbon monoxide and the alkoxycarbonylation of alkenes: the importance of Cis-coordinating phosphines.

Linear carboxylic acid esters from .alpha. olefins. 2. Catalysis by homogeneous palladium complexes

Citations

Palladium-Catalyzed Carbonylation Reactions of Alkenes and Alkynes

Organopalladium intermediates in organic synthesis

Hydrido Complexes of Palladium.

Alcoholysis of acylpalladium(II) complexes relevant to the alternating copolymerization of ethene and carbon monoxide and the alkoxycarbonylation of alkenes: the importance of Cis-coordinating phosphines.

57 – Organopalladium Compounds in Organic Synthesis and in Catalysis

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