The last 15 years of hydroformylation and carbonylation chemistry are reviewed, including technical and commercial aspects.

Progress in hydroformylation and carbonylation

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.

Palladium-Catalyzed Carbonylation Reactions of Alkenes and Alkynes

The asymmetric alkoxycarbonylation of vinylarenes catalysed by palladium complexes bearing chiral phosphine ligands has attracted much attention over the last decades. The products of both mono- and bis(alkoxycarbonylation) reactions are important intermediates in the syntheses of pharmaceuticals such as 2-arylpropionic acids, the most important class of non-steroidal anti-inflammatory drugs. In this article, a general overview of the topics will be presented and the recent advances in this field will be particularly detailed. Besides the term alkoxycarbonylation, hydroesterification and hydroalkoxycarbonylation are also used in the literature to describe this reaction. Furthermore, more specific terms such as methoxycarbonylation can be found. In this report, the term alkoxycarbonylation will be used as the general term, and specific terms will be used to unambiguously define which reaction is meant.

Pd-catalysed asymmetric mono- and bis-alkoxycarbonylation of vinylarenes

The production of low molecular weight oxygenates from carbon monoxide and ethene

https://escholarship.org/content/qt985943q6/qt985943q6.pdf?t=pn675i

Generation of the Methoxycarbonyl Radical by Visible-Light Photoredox Catalysis and Its Conjugate Addition with Electron-Deficient Olefins.

The regioselectivity of the hydro-alkoxycarbonylation of methyl acrylate, methacrylate, and crotonate catalyzed by [PdCl 2 L 2 ] complexe (L=phosphine ligands) can be largely controlled by variation of the ligands. PPh 3 promotes preferential carbonylation at the α-position, whereas with [(2,2-dimethyl-1,3-dioxolane-4,5-diyl) bis(methylene)] bis[diphenylphosphine] as ligand, the β-position is overwhelmingly carbonylated

On the Regioselectivity Control in the Palladium‐Catalyzed Hydro‐alkoxycarbonylation of α,β‐Unsaturated Esters

Pd (CO) (PPh3)3 could be isolated from the reaction mixture arising from cyclohexene hydrocarboxylation by PdCl2 (PPh3)2 as the catalyst precursor; furthermore, it has also been prepared through direct reaction of Pd (PPh3)4 with CO in benzene. For this complex, 31P- and 13C-NMR. spectra suggest a rapid dissociation of PPh3 at room temperature and a tetrahedral structure at – 70° in solution.

Fritz Wenzinger

Papers

On the Regioselectivity Control in the Palladium‐Catalyzed Hydro‐alkoxycarbonylation of α,β‐Unsaturated Esters

On the Synthesis and Characterization of Pd (CO) (PPh3)3