TBHP/NH4I-mediated Direct N−H Phosphorylation of Imines and Imidates

A direct and practical metal-free N–H phosphorylation has been achieved via the TBHP/NH4I-mediated cross-dehydrogenative coupling (CDC) reactions between imines/imidates and P(O)H compounds. This transformation provides an efficient synthetic route to the construction of P–N bonds with good functional group compatibility, leading to the formation of N-phosphorylimines and N-phosphorylimidates in up to 95% yield (33 examples) under mild conditions.