Decarboxylative Selective Phosphorylation of Aliphatic Acids: A Transition‐Metal‐ and Photocatalyst‐Free Avenue to Dialkyl and Trialkyl Phosphine Oxides from White Phosphorus

Abstract

Developing practical and mild strategies for the direct functionalization of white phosphorus (P 4 ) without chlorination is an appealing but formidable challenge. To this end, we report a breakthrough in the preparation of structurally diverse dialkylphosphines and trialkylphosphines that rely on the successive generation of carbon-centered radicals from N-hydroxyphthalimide (NHPI) esters and the controllable alkylation of the P 4 molecule under transition-metal-and photocatalyst-free conditions. To facilitate separation and prevent product losses during purification, the corresponding oxidation products dialkylphosphine oxides (DAPOs) and trialkylphosphine oxides (TAPOs) were isolated. This photoinduced phosphorylation reaction features one-pot operation, high product selectivity, and tolerates a broad range of alkyl NHPI esters, including derivatives of complex natural products and pharmaceuticals. Further diversified transformation of DAPOs to construct PÀ F, PÀ C, PÀ N, and PÀ O bonds was also demonstrated.

Photochemical Benzylation of White Phosphorus

“…12 Very recently, Tang et al reported the reaction of activated esters with P 4 under visible light to realize the synthesis of dialkyl and trialkyl phosphine oxides. 13 These two reactions involve the generation of radicals from preactivated substrates. In contrast, the generation of radicals from readily available halogenated hydrocarbons by photocatalytic reactions under mild conditions should be a good choice.…”

Cost-effective phosphates redox-neutral transformation to bench-stable phosphorylation precursor

“…Recent advancements have been promising, with the development of safer, low-energy methods for synthesizing organophosphorus compounds. One such method involves directly functionalizing white phosphorus to convert it into phosphorus-containing chemicals without the use of chlorine [23][24][25][26][27][28][29][30] .…”

Ternary Photoredox/Nickel/Halide Catalysis for the Phosphorylation of Alcohols with White Phosphorus

“…In 2019, we found the first photoredox method to synthesize phosphorotrithioites from thiols and P 4 (Scheme d) . Wolf et al conducted a pioneering study on the activation of P 4 by aryl radicals generated from readily available aryl halides under photoirradiation to access valuable triarylphosphines and tetraarylphosphonium salts (Scheme d). − In 2022, we reported the facile functionalization of P 4 by alkyl radicals from N -hydroxyphthalimide (NHPI) esters to prepare structurally diverse dialkylphosphines and trialkylphosphines under visible-light irradiation without the need for an exogenous photoredox catalyst (Scheme d) …”