Homogeneous Transition Metal Catalysis of Acceptorless Dehydrogenative Alcohol Oxidation: Applications in Hydrogen Storage and to Heterocycle Synthesis.

The different types of acceptorless alcohol dehydrogenation (AAD) reactions are discussed, followed by the catalysts and mechanisms involved. Special emphasis is put on the common appearance in AAD of pincer ligands, of noninnocent ligands, and of outer sphere mechanisms. Early work emphasized precious metals, mainly Ru and Ir, but interest in nonprecious metal AAD catalysis is growing. Alcohol-amine combinations are discussed to the extent that net oxidation occurs by loss of H2. These reactions are of potential synthetic interest because they can lead to N heterocycles such as pyrroles and pyridines. AAD also has green chemistry credentials in that an oxidation occurs without the need for an oxidizing agent and hence without the waste formation that would result from its use.