Oxidation of Organic Compounds Using Water as the Oxidant with H(2) Liberation Catalyzed by Molecular Metal Complexes

[Image: see text] Oxidation reactions of organic compounds play a central role in both industrial chemical and material synthesis as well as in fine chemical and pharmaceutical synthesis. While traditional laboratory-scale oxidative syntheses have relied on the use of strong oxidizers, modern large-scale oxidation processes preferentially utilize air or pure O(2) as an oxidant, with other oxidants such as hydrogen peroxide, nitric acid, and aqueous chlorine solution also being used in some processes. The use of molecular oxygen or air as an oxidant has been very attractive in recent decades because of the abundance of air and the lack of wasteful byproduct generation. Nevertheless, the use of high-pressure air or, in particular, pure oxygen can lead to serious safety concerns with improper handling and also necessitates the use of sophisticated high-pressure reactors for the processes. Several research groups, including ours, have investigated in recent times the possibility of carrying out catalytic oxidation reactions using water as the formal oxidant, with no added conventional oxidants. Along with the abundant availability of water, these processes also generate dihydrogen gas as the reaction coproduct, which is a highly valuable fuel. Several well-defined molecular metal complexes have been reported in recent years to catalyze these unusual oxidative reactions with water. A ruthenium bipyridine-based PNN pincer complex was reported by us to catalyze the oxidation of primary alcohols to carboxylate salts with alkaline water along with H(2) liberation, followed by reports by other groups using other complexes as catalysts. At the same time, ruthenium-, iridium-, and rhodium-based complexes have been reported to catalyze aldehyde oxidation to carboxylic acids using water. Our group has combined the catalytic aqueous alcohol and aldehyde oxidation activity of a ruthenium complex to achieve the oxidation of biomass-derived renewable aldehydes such as furfural and 5-hydroxymethylfurfural (HMF) to furoic acid and furandicarboxylic acid (FDCA), respectively, using alkaline water as the oxidant, liberating H(2). Ruthenium complexes with an acridine-based PNP ligand have also been employed by our group for the catalytic oxidation of amines to the corresponding lactams, or to carboxylic acids via a deaminative route, using water. Similarly, we also reported molecular complexes for the catalytic Markovnikov oxidation of alkenes to ketones using water, similar to Wacker-type oxidation, which, however, does not require any terminal oxidant and produces H(2) as the coproduct. At the same time, the oxidation of enol ethers to the corresponding esters with water has also been reported. This account will highlight these recent advances where water was used as an oxidant to carry out selective oxidation reactions of organic compounds, catalyzed by well-defined molecular complexes, with H(2) liberation. The oxidation of alcohols, aldehydes, amines, alkenes, and enol ethers will be discussed to provide an outlook toward other functional groups’ oxidation. We hope that this will aid researchers in devising other oxidative dehydrogenative catalytic systems using water, complementing traditional oxidative processes involving strong oxidants and molecular oxygen.