Herein, a direct C8‐oxygenation of naphthalene derivatives is described. Different carbonyl groups were used as directing group to deliver corresponding naphthols via a palladium‐catalyzed oxidation reaction using PhI(OAc)2 in a TFA/TFAA mixture. Interestingly, when Weinreb amide was employed as the directing group, the naphtholactone skeleton was directly obtained. This methodology was applied to the synthesis of variously substituted naphtholactones.
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