AbstractThe dehydrogenative synthesis of β‐damascenone from β‐damascone via the related allyl bromide intermediate was studied in depth. The requisite dehydrobromination thereof was found strongly solvent system dependent. Under respective conditions, the product was identified as dehydrogenation‐derived a, 4‐alkoxy‐derived b and 4‐oxo‐derived c, accordingly. In addition, the conversion from b to a was successfully accomplished, thereby offering an alternative access (with one step more) to reach β‐damascenone. Copyright © 2016 John Wiley & Sons, Ltd.