Catalytic Ortho-Acetoxylation of Masked Benzyl Alcohols via an Exo-Directing Mode

A Pd-catalyzed ortho-acetoxylation of masked benzyl alcohols to synthesize various 2-hydroxyalkylphenol derivatives is reported. The 2,6-dimethoxyl benzaldoxime proved to be an efficient exo-type directing group for arene (sp2) C–H functionalization. Two strategies were demonstrated to remove the directing group through N–O and C–O bond cleavages. A high catalyst turnover (>1000) was obtained to illustrate the practicality of this method.