Ni-catalyzed mild hydrogenolysis and oxidations of C–O bonds via carbonate redox tags

Abstract

Abstract Oxygenated molecules are omnipresent in natural as well as artificial settings making the redox transformation of the present C–O bonds a central tool for their processing. However, the required (super)stoichiometric redox agents which traditionally include highly reactive and hazardous reagents pose multiple practical challenges including process safety hazards or special waste management requirements. Here, we report a mild Ni-catalyzed fragmentation strategy based on carbonate redox tags for redox transformations of oxygenated hydrocarbons in the absence of any external redox equivalents or other additives. The purely catalytic process enables the hydrogenolysis of strong C(sp2)–O bonds including that of enol carbonates as well as the catalytic oxidation of C–O bonds under mild conditions down to room temperature. Additionally, we investigated the underlying mechanism and showcased the benefits of carbonate redox tags in multiple applications. More broadly, the work herein demonstrates the potential of redox tags for organic synthesis.