AbstractOn treatment with Ti(OiPr)4, 4‐hydroperoxy‐4‐methyl‐2,5‐cyclohexadien‐1‐one (1) and 10β‐hydroperoxy‐1,4‐estradiene‐3,17‐dione (3), readily available by photooxygenation ofp‐cresol and estrone, respectively, were converted to the corresponding epoxy quinols5and6a, b. Also significant amounts of the respective quinols2and4were obtained, which could be transformed in high yields into5and6a, bby Sharpless oxidation withtert‐butyl hydroperoxide using Ti(OiPr)4or VO(acac)2as catalysts. Epoxidation of the quinol4withm‐CPBA led preferentially to the lactone7by Bayer‐Villiger rearrangement, showing the advantage