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Peer-reviewedCC BY 4.0Organic Letters

Oxidative Fluorination of β-Ketoamides: Guanidinium Iodides as Iodoarene Alternatives

  • Toma Osawa
  • Hayate Ishizuka
  • Takashi Yamazaki
  • Kazuo Nagasawa
  • Dominique Cahard
Open at sourcePDFDOICite

Abstract

A guanidinium iodide-catalyzed oxidative fluorination of β-ketoamides enables umpolung α-fluorination, replacing iodoarenes with a simple iodide source. Using HF•Pyridine as the fluoride source, mCPBA as the oxidant in dichloroethane, quaternary α-fluoro-β-ketoamides are obtained in up to 92% yield with broad substrate scope, tolerating aromatic, aliphatic and acyclic systems. Mechanistic studies identify hypoiodous and/or iodous acids as the catalytic species, while the guanidinium cation enhances both solubility and reactivity.

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Cite

BibTeXRIS
BibTeX
@article{osawa2026oxidative,
  title = {{Oxidative Fluorination of β-Ketoamides: Guanidinium Iodides as Iodoarene Alternatives}},
  author = {Toma Osawa and Hayate Ishizuka and Takashi Yamazaki and Kazuo Nagasawa and Dominique Cahard},
  journal = {Organic Letters},
  year = {2026},
  month = sep,
  doi = {10.1021/acs.orglett.6c03154},
  url = {https://hal.science/hal-05746655v1},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - Oxidative Fluorination of β-Ketoamides: Guanidinium Iodides as Iodoarene Alternatives
AU  - Toma Osawa
AU  - Hayate Ishizuka
AU  - Takashi Yamazaki
AU  - Kazuo Nagasawa
AU  - Dominique Cahard
PY  - 2026
DA  - 2026/09/10
JO  - Organic Letters
DO  - 10.1021/acs.orglett.6c03154
UR  - https://hal.science/hal-05746655v1
AB  - A guanidinium iodide-catalyzed oxidative fluorination of β-ketoamides enables umpolung α-fluorination, replacing iodoarenes with a simple iodide source. Using HF•Pyridine as the fluoride source, mCPBA as the oxidant in dichloroethane, quaternary α-fluoro-β-ketoamides are obtained in up to 92% yield with broad substrate scope, tolerating aromatic, aliphatic and acyclic systems. Mechanistic studies identify hypoiodous and/or iodous acids as the catalytic species, while the guanidinium cation enhances both solubility and reactivity.
SN  - 1523-7060
SN  - 1523-7052
ER  -