Unlocking flavin photoacid catalysis through electrophotochemistry

Abstract

Molecular flavins are one of the most versatile photocatalysts. They can coordinate single and multiple electron transfer processes, gift hydrogen atoms, form reversible covalent linkages that support group transfer mechanisms, and impart photonic energy to ground state molecules, priming them for downstream reactions. But one mechanism that has not featured extensively is the ability of flavins to act as photoacids. Herein, we disclose our proof-of-concept studies showing that electrophotochemistry can transform fully oxidized flavin quinones to super-oxidized flavinium photoacids that successfully guide proton-transfer and deliver acid-catalyzed products. We also show that these species can adopt a second mechanism wherein they react with water to release hydroxyl radicals that facilitate hydrogen-atom abstraction and sp³C–H functionalization protocols. Together, this unprecedented bimodal reactivity enables electro-generated flavinium salts to affect synthetic chemistries previously unknown to flavins, greatly expanding their versatility as catalysts.