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 P−F, P−C, P−N, and P−O bonds was also demonstrated.