A photocatalytic method to selectively synthesize 4-hydroperoxy-2,5-cyclohexadienones from para-alkyl phenols is disclosed. This photosensitized singlet oxygen approach functionalized a variety of electronically diverse para-alkyl phenols in 27-99% isolated yields. Utilizing this dearomative oxidation, (±)-stemenone B and (±)-parvistilbine B were synthesized in 9 and 11 steps, respectively, from commercially available starting materials. Additional experiments revealed the dramatic influence of base and solvent on the selectivity while providing insight into the mechanism of this transformation.