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An iridium(III)-catalyzed tandem synthesis of amides and amines from esters under solvent-free conditions is described. A commercially available iridium(III) complex, [Cp*IrCl2]2, with sodium acetate showed the best activity for the synthesis of amides and secondary amines. The amide was formed by ester-amide exchange which generates an alcohol in situ which is subsequently transformed to a secondary amine via hydrogen autotransfer. This synthetic protocol with high atom economy generates water as the sole by-product and can afford amides and amines from various esters in a one-pot reaction, expanding the synthetic versatility of ester transformations. [ABSTRACT FROM AUTHOR]

An efficient, operatively simple, acceptorless, and base-free dehydrogenation of secondary alcohols and nitrogen-containing heterocyclic compounds was achieved by using readily available ruthenium hydride complexes as precatalysts. The complex RuH2(CO)(PPh3)3 ( 1) and Shvo's complex ( 2) showed excellent activities for the dehydrogenation of secondary alcohols and nitrogen containing heterocycles. In addition to complexes 1 and 2, the complex RuH2(PPh3)4 ( 3) also showed moderate to excellent activity for the acceptorless dehydrogenation of nitrogen-containing heterocyclic compounds. Kinetic studies on the oxidation reaction of 1-phenylethanol using complex 1 were carried out in the presence and the absence of external triphenylphosphine (PPh3). External addition of PPh3 had a negative influence on the rate of the reaction, which suggested that dissociation of PPh3 occurred during the course of the reaction. Hydrogen was evolved from the oxidation reaction of 1-phenylethanol by using 1 mol% of 1 (88%) and 2 (92%), which demonstrated the possible usage of the catalytic systems in hydrogen generation. [ABSTRACT FROM AUTHOR]

An abstract of the article "Tandem Synthesis of Amides and Secondary Amines from Esters with Primary Amines under Solvent-Free Conditions" is presented.

Shov′s complex Ru2(CO)4(C5Ph4OH)2 shows the best activity for the oxidation of both secondary alcohols and nitrogen-containing heterocyclic compounds amongst other tested ruthenium-hydride complexes. [ABSTRACT FROM AUTHOR]