The oxidation of (5-acyloxypent-3-enyl)benzene with hypervalent iodine(III) afforded 2-oxy-1-(oxymethyl)tetrahydronaphthalene under metal-free conditions. The acyloxy group may nucleophilically participate in the oxidative cyclization. A lactate-based chiral hypervalent iodine afforded an enantioselective variant of oxyarylation with up to 89% ee.