Intramolecular Phenol Dearomatizations

I. We have developed an acid-promoted dearomative rearrangement of O-arylhydroxylamines that form 2-aminocyclohexadien-1-ones, which can be reductively quenched for the synthesis of trans-aminoalcohols on a cyclohexadiene core. These hydroxylamines can be synthesized from commercial or readily prepared 2-aryl phenols. II. We report a dearomative Claisen rearrangement of a phenol ether driven by the concomitant aromatization of nosyl-protected 1,2,3-triazoles. Nosyl azide reacts in a [3+2] cycloaddition with aryloxyallenes before undergoing the transfer dearomatization. The aryloxyallenes can be synthesized in two steps from readily available phenols.