Synchronous recognition of P–intermediates and nucleophiles empowers diversified trivalent phosphorus synthesis

Abstract

Trivalent phosphines bearing P–X bonds are valuable intermediates, antioxidants, ligands, and functional agents, yet their sustainable and selective synthesis remains challenging. Here we present a synchronous identification strategy for P-intermediates and nucleophiles that enables oxidant-free electrochemical P–H/X–H cross-coupling to P(III) phosphines. Combined CV, EPR, 31P NMR sampling, and in-situ mass spectrometry analyses reveal the stepwise conversion of P–H species into P-centered radicals, bisphosphine intermediates, and bisphosphine radical cations intermediates. These intermediates are selectively recognized by N–H, S–H, or O–H nucleophiles, directing the formation of P–N, P–S, and P–O bonds. One to three P–X bonds can be installed in a single operation from diverse X–H partners, affording bi- and multidentate trivalent phosphines with high selectivity. This mechanistically guided platform offers a sustainable and programmable route to functional trivalent phosphorus, thereby broadening the synthetic toolbox for trivalent phosphorus design.