Amides are synthesized directly from alcohols and amines in high yields using an in situ generated catalyst from easily available ruthenium complexes such as the (p-cymene, an N-heterocyclic carbene (NHC) ligand, and a nitrogen containing L-type ligand such as acetonitrile. The phosphine-free catalyst systems showed improved or comparable activity compared to previous phosphine-based catalytic systems. The in situ generated catalyst from [RuA C H T U N G T R E N N U N G (benzene)Cl 2 ] 2 , an NHC ligand, and acetonitrile showed excellent activity toward reactions with cyclic secondary amines such as piperidine and morpholine.

An in situ generated catalyst from readily available RuH(2)(PPh(3))(4), an N-heterocyclic carbene (NHC) precursor, NaH, and acetonitrile was developed. The catalyst showed high activity for the amide synthesis directly from either alcohols or aldehydes with amines. When a mixture of an alcohol and an aldehyde was reacted with an amine, both of the corresponding amides were obtained with good yields. Homogeneous Ru(0) complexes such as (eta(4)-1,5-cyclooctadiene)(eta(6)-1,3,5-cyclooctatriene)ruthenium [Ru(cod)(cot)] and Ru(3)(CO)(12) were also active in the amidation of an alcohol or an aldehyde with the help of an in situ generated NHC ligand.

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 RuH 2 (CO)A C H T U N G T R E N N U N G (PPh 3 ) 3 (1) and Shvos complex (2) showed excellent activities for the dehydrogenation of secondary alcohols and nitrogen containing heterocycles. In addition to complexes 1 and 2, the complex RuH 2 A C H T U N G T R E N N U N G (PPh 3 ) 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-phe-nylethanol using complex 1 were carried out in the presence and the absence of external triphenylphosphine (PPh 3 ). External addition of PPh 3 had a negative influence on the rate of the reaction, which suggested that dissociation of PPh 3 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.

There′s something imide so strong: Cyclic imides were synthesized from simple diols with primary amines in a single step using an in‐situ‐generated ruthenium catalytic system. The atom‐economical and operatively simple syntheses of succinimides, phthalimides, and glutarimides, which are important building blocks in natural products and drugs, was also demonstrated.

The synthetic viability of several N-heterocyclic carbene-stabilized dichloroborenium cations [NHCBCl 2 ] + (NHC = (RC) 2 (NR') 2 C;