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Anilides are often found in pharmaceuticals and active ingredients in crop protection. Although of great interest, the atom‐ and step economic formation of the amide bond between a less nucleophilic aniline with an acid or ester remains still a major challenge. Herein, we report an aminolysis of aromatic and alkyl esters with anilines catalyzed by a readily available catalytic system comprising of an earth‐abundant Mn‐salt in combination with an inexpensive base. [ABSTRACT FROM AUTHOR]

The use of carbon dioxide (CO2) as a building block in organic synthesis is a topic of high interest. We here reflect from an industrial perspective, which of the approaches may have the potential to be applied in the near future in industrial organic synthesis on a significant scale. Drawbacks to overcome and challenges to be addressed are also discussed in this critical review. This review focuses on systems providing a high atom‐efficiency and which could be competitive to other state‐of‐the art syntheses. [ABSTRACT FROM AUTHOR]

Sodium acrylate is a valuable monomer for the synthesis of superabsorbents and produced industrially on large scale. Currently, sodium acrylate is made by the oxidation of propene to acrylic acid followed by neutralization with NaOH. The synthesis of sodium acrylate from CO2, ethylene, and NaOH would be very attractive due to lower raw material costs but was for many years only a "dream reaction." Significant progress has been made since the first report in 2012 on a catalytic system for this synthesis. Different nickel and palladium catalysts were identified. In addition, the influence of the base in this reaction was evaluated. The use of solvents fulfilling certain criteria is necessary for the design of continuous process concepts. To date, two process concepts have resulted: one using phenolate bases and the other utilizing alkoxide bases. [ABSTRACT FROM AUTHOR]

A cooperative methoxy transfer between orthosilicate esters and organotin oxides was developed for the synthesis of various N-alkyl and N-aryl carbamates from carbon dioxide in up to 97% isolated yield. The reaction is highly selective and N-alkylated amines are not observed. Density functional theory calculations of the reaction were performed and, together with NMR observations, a plausible mechanism featuring the catalytic regeneration of dialkyltin dialkoxide is proposed. [ABSTRACT FROM AUTHOR]

The carboxylation of olefins beyond ethylene towards α,β-unsaturated carboxylic acid salts and a detailed investigation on the critical steps in the catalysis are reported. The influence of two chelating phosphine ligands and several olefins on the elemental steps of the catalysis is shown. The work focusses on the formation of intermediate olefin complexes, lactone formation and base induced elimination of the lactone. The direct carboxylation of olefins is possible using nickel catalysts, which opens a new route towards the desired α,β-unsaturated carboxylic acid salts. The reaction works particularly well for 1,3-dienes and proceeds via the formation of allyl-carboxylates. The ability to form such allyl-type lactone complexes seems in this case to be the most challenging step towards satisfactory turnover numbers. [ABSTRACT FROM AUTHOR]

A graphical abstract of the article "Direct Synthesis of Primary Amines via Ruthenium-Catalyzed Amination of Ketones with Ammonia and Hydrogen" is presented.