A transition-metal free synthesis of highly functionalized 2-hydroxy-2′-amino-1,1′-biaryls from N-arylhydroxylamines has been developed. This operationally simple and readily scalable approach relies on a cascade of reactions that initially generates transient N,O-diarylhydroxylamines, via direct O-arylation, which then undergo rapid [3,3]-sigmatropic rearrangement and subsequent rearomatization to