Year: 2026
Type: preprint
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.
Source: ChemRxiv
Institution: University College Dublin
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7212041338