Paired Electrolysis-Driven P(O)-N Bond Formation via Reductive Cross-Coupling of Nitroarenes with Phosphine Oxides

The efficient construction of the P(O)-N bond is crucial in organic synthesis. P(O)-N bond formations with nitroarenes and phosphine oxides were accomplished via paired electrolysis-promoted reductive cross-coupling reactions under metal-catalyst- and chemical-reductant-free conditions. The combination of paired electrolysis with reductive coupling enabled P(O)-N bond formation in a chemo-selective fashion and exhibited broad functional group tolerance, which allows for the synthesis of phosphinamides, phosphonamides, and phosphoramides and provides access to late-stage functionalization. Mechanistic studies indicated that both radical and Atherton-Todd pathways are operative in the electro-reductive coupling.