Synthesis of ortho-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 ortho-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.