Palladium-catalyzed carbonylation reactions of aromatic halides in the presence of various nucleophiles have undergone rapid development since the pioneering work of Heck and co-workers in 1974, such that nowadays a plethora of palladium catalysts are available for different carbonylative transformations. The carboxylic acid derivatives, aldehydes, and ketones prepared in this way are important intermediates in the manufacture of dyes, pharmaceuticals, agrochemicals, and other industrial products. In this Review, the recent academic developments in this area and the first industrial processes are summarized.

Palladium-catalyzed carbonylation reactions of aryl halides and related compounds.

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

Progress in hydroformylation and carbonylation

Palladium-Catalyzed Carbonylation—A Reaction Come of Age

Um eine CO-Gruppe reicher: (Hetero-)Arene sind aus der industriellen Herstellung von Agrochemikalien, Farbstoffen, Pharmaka etc. nicht wegzudenken. Wahrend der vergangenen Jahrzehnte wurden ubergangsmetallkatalysierte Kupplungen von Arylhalogeniden mit Nucleophilen aller Art entwickelt. Dieser Aufsatz fasst aktuelle Fortschritte auf dem Gebiet der palladiumkatalysierten Carbonylierungen von Arylhalogeniden und ahnlichen Verbindungen zusammen (siehe Schema).

Palladiumkatalysierte Carbonylierungen von Arylhalogeniden in Gegenwart verschiedener Nucleophile haben sich seit ihrer Einfuhrung durch Heck und Mitarbeiter im Jahr 1974 schnell weiterentwickelt, sodass heute eine Vielzahl von Palladiumkatalysatoren fur unterschiedliche Carbonylierungsreaktionen verfugbar ist. Auf diesem Weg erhaltliche Carbonsaurederivate, Aldehyde und Ketone sind wichtige Zwischenstufen bei der industriellen Herstellung von Farbstoffen, Pharmaka, Agrochemikalien und anderen Produkten. In diesem Aufsatz werden aktuelle Ergebnisse aus der akademischen Forschung und erste industrielle Prozesse zusammengefasst.

Palladiumkatalysierte Carbonylierungen von Arylhalogeniden und ähnlichen Substraten

Recently, carbonylation reactions have gained considerable interest as they are becoming a versatile tool in the synthesis of pharmaceuticals, agrochemicals and their intermediates. Nowadays, a plethora of transition metal catalysts are available for the synthesis of various functional groups like ureas, carbamates, oxamates, oxamides, α-keto amides, ketones, esters, etc. using carbonylation methodology. Several carbonylation reactions such as aminocarbonylation, alkoxycarbonylation, double carbonylation and oxidative carbonylation, provide efficient and attractive alternatives to the conventional synthetic routes on a laboratory or industrial scale. Oxidative carbonylation is an important reaction as it allows direct carbonylative C–H bond activation. A double carbonylation reaction provides a one step alternative route for the synthesis of α-keto amides, oxamides, and oxamates. It also eliminates the use of conventional thermally unstable and toxic reagents like oxalyl chloride. Several recent studies have focused on the various aspects of these reactions, including catalyst–product separation, and catalyst recoverability and reusability. In view of this, developments in anchoring homogeneous catalysts using various techniques like biphasic catalysis and supported liquid phase catalysis are gaining importance. Carbonylation routes using these techniques are simple, efficient, economical, avoid the use of ligands, and give the desired products in excellent yields. The use of phosphine ligands is disadvantageous as it leads to air/moisture sensitivity, tedious work-up procedures and high work-up costs. Several phosphine-free carbonylation routes eliminate the use of phosphine ligands, and provide economical and simple methods for these transformations. In this review we have summarized the recent trends in carbonylative transformations, which have undergone a rapid development.

/pdf/recent-developments-in-palladium-catalysed-carbonylation-2il9jv33tq.pdf

Recent developments in palladium catalysed carbonylation reactions

Divers halogenures d'aryles sont convertis catalytiquement en α-cetoamides et amides par traitement avec des amines secondaires et le monoxyde de carbone

Hidehiko Soyama

Papers

Palladium-catalyzed double carbonylation of aryl halides to give .alpha.-keto amides. Mechanistic studies