The [1,3]-nitrogen rearrangement reactions of O-aryl ketoximes were promoted by N-heterocyclic carbene (NHC)-copper catalysts and BF3·OEt2 as an additive, affording ortho-aminophenol derivatives in good yields. The reaction of substrates with electron-withdrawing substituents on the phenol moiety are accelerated by adding silver salt and modifying the substituent at the nitrogen atom. Density functional theory calculations suggest that the rate-determining step of this reaction is the oxidative addition of the N-O bond of the substrate to the copper catalyst. The negative ρ values of the substituent at both the oxime carbon and phenoxy group indicate that the donation of electrons by the oxygen and nitrogen atoms accelerates the oxidative addition.
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