Synthesis of Phosphinic Amides from Chlorophosphines and Hydroxyl Amines via P(III) to P(V) Rearrangement
Fang Cheng, Dongqiu Li, Jing Li, Yuhai Tang, Yong Wu, Silong Xu
Abstract
Phosphoranyl radicals are essential mediators to bring about new radicals but often produce a stoichiometric amount of phosphine oxide/sulfide waste. Herein, we devised a phosphorus-containing species as a radical precursor, but without the generation of phosphorus waste. Accordingly, a catalyst-free synthesis of phosphinic amides from hydroxyl amines and chlorophosphines via P(III) to P(V) rearrangement is described. Mechanistically, it may involve the initial formation of a R 2 N–O–PR 2 species that undergoes homolysis of N–O bonds and subsequent radical recombination.
Topics & Concepts
ChemistryHomolysisRadicalPhosphine oxidePhosphineMedicinal chemistryCatalysisPhosphorusSulfideStoichiometryDeoxygenationOrganic chemistryPhotochemistryAsymmetric Hydrogenation and CatalysisChemical Synthesis and ReactionsSulfur-Based Synthesis Techniques