The hydrogenation of aliphatic nitriles over Pd/C, Pd/Al2O3, and Pd−Au/Al2O3 catalysts were evaluated for the selective hydrogenation of aliphatic nitriles to the corresponding primary amines. The highest selectivity (>99%) toward primary amines was achieved when the reaction was carried out in acetic acid using 10 mol% of 25% Pd‐5% Au/Al2O3 under relatively low hydrogen pressure (0.8 MPa). Characterization of the catalysts by XRD, CO adsorption experiments, and EXAFS revealed that the excellent selectivity of 25% Pd‐5% Au/Al2O3 toward the synthesis of primary amines is determined by the electronic properties and/or the surface structure resulting from alloying Pd with Au.magnified image

10% Palladium on carbon (10% Pd/C) successfully catalyzed the intramolecular C À Ha mination of various N-mesylated 2-aminobiphenyls in the presence of ac atalytic amount of pyridine Noxide in heated dimethyl sulfoxide (DMSO) under an oxygena tmosphere to afford the corresponding N-mesylcarbazoles.T he reactionw ould proceed via asingle-electron transfer process based on its significant suppression by the addition of as ingle-electron scavenger, tetracyanoquinodimethane (TCNQ), andt he substituents on the aromatic rings of the substrate have an insignificante ffect on the reaction progress.

A new ruthenium on carbon-catalysed carbon-carbon (CÀC) cleavage reaction of aryl alkyl ketone derivatives in water in the presence of CaO under atmospheric oxygen conditions has been developed. Corresponding benzoic acid derivatives were produced from various aryl alkyl ketones in excellent yields. CaO acts as an adsorbent of CO and CO 2 to maintain a sufficient concentration of oxygen around the catalyst required for effective progress of the reaction. It was also revealed that aliphatic aldehydes were generated from the alkyl moiety of aryl alkyl ketones over the course of the reaction. The aliphatic aldehyde derivatives undergo either an oxidation to the corresponding aliphatic carboxylic acids or a further continuous CÀC cleavage reaction to form aliphatic aldehydes with loss of one carbon along with the formation of CO and CO 2 .