Benchmarking Trisaminocyclopropeniums as Mediators for Anodic Oxidation Reactions

• DOI: 10.1021/acs.joc.4c00422
• Publication Date: 2024-04-12T17:01:13Z
• Authors: Sabrina N. Carneiro; Joshua D. Laffoon; Long Luo; Melanie S. Sanford
• Keywords: Anodic oxidation

This report benchmarks a tris(amino)cyclopropenium (TAC) salt as an electron-transfer mediator for anodic oxidation reactions in comparison to two known mediators: triarylamine and triarylimidazole derivative. The three mediators have redox potentials, diffusion coefficients, heterogeneous electron transfer rates similar those of glassy carbon electrodes acetonitrile/KPF6. However, they differ significantly their performance electro-organic reactions: fluorination dithiane 4-methoxybenzyl alcohol. These differences are rationalized based on variable stability the presence reaction components (e.g., NEt3·3HF, lutidine, Cs2CO3) well very different with organic substrate. Overall, this work highlights advantages disadvantages each provides foundation expanding applications TACs synthesis moving forward.