Synthesis of <i>ortho</i>-Phosphated (Hetero)Arylamines through Cascade Atherton-Todd Reaction/[3,3]-Rearrangement from Arylhydroxylamines and Dialkyl Phosphites.

A practical and facile strategy for the synthesis of <i>ortho</i>-phosphated (hetero)arylamines from readily available arylhydroxylamines and dialkyl phosphites via cascade Atherton-Todd reaction/[3,3]-rearrangement was developed. This method is amenable to various arylhydroxylamines such as phenylhydroxylamines, naphthylhydroxylamines, and pyridylhydroxylamines, has mild reaction conditions, is oxidant-free, and has good functional-group compatibility and excellent regioselectivity.