Here, we report a synthetic approach for a wide range of unsymmetrical alkylphosphorus(V) compounds, alkyl-P(O)XY (X ≠ Y) using imidazolium phosphonites as bifunctional reagents. This protocol consists of two sequences, C(sp³)–P bond formation via an organic photoredox-catalyzed decarboxylative alkylation of imidazolium phosphonites with aliphatic carboxylic acid derivatives and P–X (X = O, N, F, S) bond formation via the S_NP(V) reaction. In this process, the imidazolium group facilitates 1) radical addition to the phosphonite reagent by stabilizing the resulting phosphoranyl radical intermediate and 2) the S_NP(V) reaction as a good leaving group. This protocol allows the introduction of primary, secondary and tertiary alkyl substituents and various heteroatom substituents onto P(V) scaffolds.
DOI: 10.1002/anie.202502803