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PreprintCC BY-NC-NDChemRxiv

μ-Oxo-Bridged Iodine(III) Reagents Enable Catalyst- and Light-Free Fluoro(halo)methyl Radical Generation

  • Anupam Das1
  • Nagarajan Ramkumar1
  • Artis Kinēns1
  • Sergey Belyakov1
  • Andris Antuzevičs2,3
  • Janis Veliks1
  1. 1National Institute of Research and Innovation
  2. 2Institute of Solid State Physics
  3. 3University of Latvia
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Abstract

While conventional radical fluoroalkylation typically requires exogenous catalysts or photoactivation to overcome significant kinetic barriers, here we report bench-stable μ-oxo-bridged iodine(III) reagents that release fluoro(halo)methyl radicals upon heating without an external catalyst, additive, or light. The resulting radicals initiate cascade cyclizations of methacrylamides and methacrylohydrazides to afford fluorinated oxindoles, pyrazolones, and related heterocycles. Variation of the fluorinated carboxylate ligand within the iodine(III) reagent framework controls the identity of the transferred C1 fragment, thereby providing chlorofluoromethyl, bromofluoromethyl, difluoromethyl, and monofluoromethyl products from a common reagent architecture. The transformation is compatible with structurally diverse and natural-product-derived substrates and proceeds efficiently upon scale-up. By encoding the required bond lability directly into the iodine(III) framework, this strategy establishes a general platform for the catalyst-, additive-, and light-free generation and incorporation of fluorinated C1 radicals into complex molecular frameworks.

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Cite

BibTeXRIS
BibTeX
@misc{das2026μoxobridged,
  title = {{μ-Oxo-Bridged Iodine(III) Reagents Enable Catalyst- and Light-Free Fluoro(halo)methyl Radical Generation}},
  author = {Anupam Das and Nagarajan Ramkumar and Artis Kinēns and Sergey Belyakov and Andris Antuzevičs and Janis Veliks},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15009392/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009392/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - μ-Oxo-Bridged Iodine(III) Reagents Enable Catalyst- and Light-Free Fluoro(halo)methyl Radical Generation
AU  - Anupam Das
AU  - Nagarajan Ramkumar
AU  - Artis Kinēns
AU  - Sergey Belyakov
AU  - Andris Antuzevičs
AU  - Janis Veliks
PY  - 2026
DA  - 2026/09/23
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009392/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009392/v1
AB  - While conventional radical fluoroalkylation typically requires exogenous catalysts or photoactivation to overcome significant kinetic barriers, here we report bench-stable μ-oxo-bridged iodine(III) reagents that release fluoro(halo)methyl radicals upon heating without an external catalyst, additive, or light. The resulting radicals initiate cascade cyclizations of methacrylamides and methacrylohydrazides to afford fluorinated oxindoles, pyrazolones, and related heterocycles. Variation of the fluorinated carboxylate ligand within the iodine(III) reagent framework controls the identity of the transferred C1 fragment, thereby providing chlorofluoromethyl, bromofluoromethyl, difluoromethyl, and monofluoromethyl products from a common reagent architecture. The transformation is compatible with structurally diverse and natural-product-derived substrates and proceeds efficiently upon scale-up. By encoding the required bond lability directly into the iodine(III) framework, this strategy establishes a general platform for the catalyst-, additive-, and light-free generation and incorporation of fluorinated C1 radicals into complex molecular frameworks.
ER  -