Catalytic Phosphorus-Based Hydrogen Atom

Abstract

We report the first catalytic phosphorus-based hydrogen atom transfer system. Using an iridium photocatalyst and 10 mol% diphenylphosphine sulfide, we achieve decarboxylative reduction of diverse carboxylic acids—including peptides and pharmaceuticals—to C–H products in up to 95% yield, without stoichiometric reductants. Mechanistic studies reveal an unprecedented anionic relay: a phosphoryl radical is reduced to a phosphinoyl anion, which upon protonation regenerates the P–H catalyst. This work establishes catalytic turnover in phosphorus-based HAT and identifies a new elementary step in main-group radical chemistry.

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BibTeX

@misc{avinash2026catalytic,
  title = {{Catalytic Phosphorus-Based Hydrogen Atom}},
  author = {Pratik Avinash and Kayla Merrigan and Bartosz Bieszczad},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008559/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008559/v1},
  note = {CC BY},
}

RIS

TY  - UNPB
TI  - Catalytic Phosphorus-Based Hydrogen Atom
AU  - Pratik Avinash
AU  - Kayla Merrigan
AU  - Bartosz Bieszczad
PY  - 2026
DA  - 2026/09/09
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008559/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008559/v1
AB  - We report the first catalytic phosphorus-based hydrogen atom transfer system. Using an iridium photocatalyst and 10 mol% diphenylphosphine sulfide, we achieve decarboxylative reduction of diverse carboxylic acids—including peptides and pharmaceuticals—to C–H products in up to 95% yield, without stoichiometric reductants. Mechanistic studies reveal an unprecedented anionic relay: a phosphoryl radical is reduced to a phosphinoyl anion, which upon protonation regenerates the P–H catalyst. This work establishes catalytic turnover in phosphorus-based HAT and identifies a new elementary step in main-group radical chemistry.
ER  -

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