Abstract“Epimestranol” (6) has been prepared from the 16α,17‐epoxide5by reduction with LiAlH4. The structures of several by‐products have been elucidated and a mechanism for their formation is discussed. Both “mestranol” (3) and “epimestranol” failed to formp‐tosylates and only “mestranol” could be converted into thep‐toluenesulfinate which readily rearranged to the allenic sulfone14. “Epimestranol” was transformed into a mixture of the two epimeric 17‐sulfone