24th International Conference on Phosphorus Chemistry (ICPC24)

129 / 2023-10-13 12:51:05

Photoinduced Decarboxylative Radical Phosphinylation

radicals, phosphorylation, decarboxylation, photoredox catalysis, radical–polar crossover

New Technologies in Phosphorus Chemistry > 1) New reagents and methods in organophosphorus Chemistry

Reported herein is an unprecedented protocol for C(sp³)–phosphinylation. With 1,2,3,5-tetrakis(cabazol-9-yl)-4,6-dicyano-benzene (4CzIPN) as the catalyst, the visible light-induced reaction of redox-active esters of aliphatic carboxylic acids with dimethyl arylphosphonites or diethyl alkylphosphonites at room temperature provides the corresponding decarboxylative phosphinylation products in satisfactory yields. The protocol exhibits broad substrate scope and wide functional group compatibility, enabling the rapid synthesis of bioactive phosphinic acids such as glutamine synthetase Glufosinate and kynureninase inhibitor. A radical–polar crossover mechanism involving the formation and subsequent oxidation of phosphoranyl radicals followed by nucleophilic demethylation (or deethylation) is proposed.