Abstract

The Electron-Coupled-Proton Buffer (see: Nature Chem. 2013, 5, 403-409; Nature Chem. 2018, 10, 1042-1047; Joule, 2018, 2, 1390-1395) permits the electrochemical oxygen evolution reaction from water to be coupled to the reversible reduction and protonation of a redox mediator (rather than the coupling of the oxygen evolution reaction directly with hydrogen production). Careful selection of this redox mediator, along with judicious choice of the electrode material for the cathode reaction, can allow reduced species to be generated that are thermodynamically unstable with respect to hydrogen generation (Science, 2014, 345, 1326-1330). These reduced mediators can either be used for spontaneous hydrogen generation (decoupled from the oxygen evolution step), or they can be used as soluble sources of hydrogen for performing the hydrogenation of organic molecules (Chem. Commun. 2018, 54, 1093-1096). In this talk, we such discuss current progress and potential future avenues for the use of Electron-Coupled-Proton Buffers as reducing equivalents in organic synthesis.

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