Direct C-H transformation via iron catalysis.

Large-scale applications of transition metal-catalyzed couplings for the synthesis of pharmaceuticals.

The coupling of aryl or vinyl halides with terminal acetylenes catalysed by palladium and other transition metals, commonly termed as Sonogashira cross-coupling reaction, is one of the most important and widely used sp2–sp carbon–carbon bond formation reactions in organic synthesis, frequently employed in the synthesis of natural products, biologically active molecules, heterocycles, molecular electronics, dendrimers and conjugated polymers or nanostructures. This critical review focuses on developments in the Sonogashira reaction achieved in recent years concerning catalysts, reaction conditions and substrates (352 references).

Recent advances in Sonogashira reactions

Flow chemistry involves the use of channels or tubing to conduct a reaction in a continuous stream rather than in a flask Flow equipment provides chemists with unique control over reaction parameters enhancing reactivity or in some cases enabling new reactions This relatively young technology has received a remarkable amount of attention in the past decade with many reports on what can be done in flow Until recently, however, the question, “Should we do this in flow?” has merely been an afterthought This review introduces readers to the basic principles and fundamentals of flow chemistry and critically discusses recent flow chemistry accounts

The Hitchhiker's Guide to Flow Chemistry

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.

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

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

Pd(OAc)2/di-1-adamantyl-n-butylphosphine (cataCXium A) is highly active in the three-component Suzuki carbonylation and represents the most general catalyst system reported up to now. A broad range of aryl/heteroaryl bromides and aryl boronic acids can be coupled to the corresponding diarylketones at low catalyst loadings.

A general synthesis of diarylketones by means of a three-component cross-coupling of aryl and heteroaryl bromides, carbon monoxide, and boronic acids.

A general palladium-catalyzed alkoxycarbonylation of aryl and heteroaryl bromides has been developed in the presence of bulky monodentate phosphines. Studies of the butoxycarbonylation of three model substrates revealed the advantages of di-1-adamantyl-n-butylphosphine compared to other ligands. In the presence of this catalyst system various bromoarenes provided the corresponding benzoic acid derivatives (ester, amides, acids) in excellent yield at low catalyst loadings (0.5 mol % Pd or below).

Anne Brennführer

Papers

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

Palladium-Catalyzed Carbonylation Reactions of Alkenes and Alkynes

Palladiumkatalysierte Carbonylierungen von Arylhalogeniden und ähnlichen Substraten

A general synthesis of diarylketones by means of a three-component cross-coupling of aryl and heteroaryl bromides, carbon monoxide, and boronic acids.

Efficient Carbonylation of Aryl and Heteroaryl Bromides using a Palladium/Diadamantylbutylphosphine Catalyst