Photoredox catalysis has emerged as a valuable alternative to dark-state catalysis. For the full potential of photoredox catalysis to be utilized, it is imperative to make use of low-energy photons in photoinduced radical processes. We have demonstrated that the use of oxalate as a coreactant provides a useful principle for the photocatalytic production of trifluoromethyl radicals (•CF3) from CF3I upon green or red LED photoirradiation of narrow-bandgap photocatalysts. The photocatalytic cycle involves a radical anion of carbon dioxide (CO2•-) as a reductant for CF3I, which is generated through photoinduced oxidative decarboxylation of oxalate. Electrochemical characterizations and steady-state and transient photophysical investigations were performed to reveal that there are two photoinduced electron-transfer pathways for oxalate-mediated •CF3 generation.
|Number of pages||8|
|Journal||Journal of Organic Chemistry|
|Publication status||Published - 2016 Aug 19|
Bibliographical noteFunding Information:
Y.Y. acknowledges a grant from the Ewha Womans University (1-2015-0447-001-1).
© 2016 American Chemical Society.
All Science Journal Classification (ASJC) codes
- Organic Chemistry