Abstract: The mammalian pheromone 5α-androst-16-en-3-one(Ⅰ) was synthesized from epiandrosterone(Ⅲ) via tosyl hydrazone(Ⅳ) followed by reduction with lithium aluminum hydride and oxidation with CrO₃-H₂SO₄ reagent. 5α-Androst-16-en-3α-ol(Ⅱ) was obtained with the same partial approach from androsterone (Ⅶ), which can be prepared from epiandrosterone(Ⅲ) via the inversion of the configuration of the C₃OH from its tosylate(Ⅵ) with sodium nitrite in DMF.