Benchmarking Trisaminocyclopropeniums as Mediators for Anodic Oxidation Reactions.

This report benchmarks a tris(amino)cyclopropenium (TAC) salt as an electron-transfer mediator for anodic oxidation reactions in comparison to two known mediators: a triarylamine and a triarylimidazole derivative. The three mediators have redox potentials, diffusion coefficients, and heterogeneous electron transfer rates similar to those of glassy carbon electrodes in acetonitrile/KPF 6 . However, they differ significantly in their performance in two electro-organic reactions: anodic fluorination of a dithiane and anodic oxidation of 4-methoxybenzyl alcohol. These differences are rationalized based on variable stability in the presence of reaction components (e.g., NEt 3 ·3HF, lutidine, and Cs 2 CO 3 ) as well as very different rates of electron transfer with the organic substrate. Overall, this work highlights the advantages and disadvantages of each mediator and provides a foundation for expanding the applications of TACs in electro-organic synthesis moving forward.