9-(4-Halo-2,6-xylyl)-10-methylacridinium Ion as an Effective Photoredox Catalyst for Oxygenation and Trifluoromethylation of Toluene Derivatives

Kei Ohkubo, Soichiro Matsumoto, Haruyasu Asahara, Shunichi Fukuzumi

Research output: Contribution to journalArticlepeer-review

Abstract

9-(2,6-Dimethylphenyl)-10-methylacridinium perchlorate ([Acr+-Xyl]ClO4-), 9-(4-chloro-2,6-dimethylphenyl)-10-methylacridinium perchlorate ([Acr+-XylCl]ClO4-), and 9-(4-fluoro-2,6-dimethylphenyl)-10-methylacridinium perchlorate ([Acr+-XylF]ClO4-) were synthesized by the Grignard reaction. The one-electron reduction potentials (Ered vs SCE) of Acr+-Xyl, Acr+-XylCl, and Acr+-XylF in deaerated acetonitrile (MeCN) were determined by cyclic voltammetry to be nearly the same as −0.55, −0.53, and −0.53 V, respectively. On the other hand, the one-electron oxidation potentials (Eox vs SCE) of Acr+-Xyl, Acr+-XylF, and Acr+-XylCl were determined by the second-harmonic alternative current voltammetric method to be +2.15, +2.20, and +2.21 V, respectively. The Eox value of Acr+-XylCl is higher than the Eox value of toluene (+2.20 V). Thus, photocatalytic oxygenation of toluene with oxygen occurs efficiently via electron transfer from toluene to the XylCl•+ moiety of the triplet electron-transfer state of Acr+-XylCl under photoirradiation of Acr+-XylCl in oxygen-saturated MeCN. By contrast, no oxygenation of toluene occurred with the 9-mesityl-10-methylacridinium ion (Acr+-Mes) used as a photocatalyst due to the lack of oxidizing ability to oxidize toluene. The metal-free trifluoromethylation of toluene derivatives has also been made possible by using Acr+-XylCl as a photocatalyst and S-(trifluoromethyl)dibenzothiophenium (CF3DBT+) as a trifluoromethyl source. The photocatalytic reaction mechanism was clarified by transient absorption and electrochemical measurements.

Original languageEnglish
Pages (from-to)2671-2684
Number of pages14
JournalACS Catalysis
Volume14
Issue number4
DOIs
StatePublished - 16 Feb 2024

Bibliographical note

Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.

Keywords

  • C-H activation
  • acridinium
  • electron transfer
  • organocatalyst
  • photooxygenation
  • photoredox catalyst
  • radical
  • trifluoromethylation

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