Scalable, transition-metal-free direct oxime O-arylation: rapid access to O-arylhydroxylamines and substituted benzo[b]furans.

O-aryloximes, generated from readily available and inexpensive oximes through transition-metal-free O-arylation, can either be hydrolyzed to O-arylhydroxylamines or conveniently converted to structurally diverse benzo[b]furans through an environmentally benign, one-pot [3,3]-sigmatropic rearrangement/cyclization sequence.