X-ray crystallographic data; detailed optimization and sensitivity tables; further discussion of mechanism and scope; cyclic voltammetry (CV) measurements; experimental procedures, detailed description of set-up, characterization data and copies of 1 H, 13 C, 19 F and 31 P NMR spectra CCDC 2184087-2184092 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. Raw and processed characterization data for all novel compounds, raw and processed data of and cartesian coordinates from computed structures can be found at Applications of Proton-Coupled Electron Transfer in Organic Synthesis. Chem. Rev. 2022, 122, 2017-2291. (55) A measured cyclic voltammogram of cyclohexene methyl carboxylate showed an oxidation at 2.12 V vs SCE but no significant reduction waves up to -3.0 V. See Supporting Figure and Supporting Table .