Reaction of H(2) with mitochondria-relevant metabolites using a multifunctional molecular catalyst

The Krebs cycle is the fuel/energy source for cellular activity and therefore of paramount importance for oxygen-based life. The cycle occurs in the mitochondrial matrix, where it produces and transfers electrons to generate energy-rich NADH and FADH(2), as well as C(4)-, C(5)-, and C(6)-polycarboxylic acids as energy-poor metabolites. These metabolites are biorenewable resources that represent potential sustainable carbon feedstocks, provided that carbon-hydrogen bonds are restored to these molecules. In the present study, these polycarboxylic acids and other mitochondria-relevant metabolites underwent dehydration (alcohol-to-olefin and/or dehydrative cyclization) and reduction (hydrogenation and hydrogenolysis) to diols or triols upon reaction with H(2), catalyzed by sterically confined iridium–bipyridyl complexes. The investigation of these single–metal site catalysts provides valuable molecular insights into the development of molecular technologies for the reduction and dehydration of highly functionalized carbon resources.