In summary, we have achieved the first synthesis of the enantiomer of naturally occurring aquilanol A (1) and its further oxidized congener aquilanol B (2), in three chemical steps starting from easily accessible (-)-caryophyllene oxide (11). Our strategy consists of an electrophilic activation of the exocyclic double bond on 11, accompanied by a retro-cycloisomerization event to obtain the eleven-membered monocyclic intermediate bromide 13 and, after hydrolysis, alcohol ent-4. Intramolecular acid catalyzed epoxide opening on the (Z)-allylic alcohol precursor completes the synthesis (overall yield 24%), thus providing a logical basis to support the biosynthetic hypothesis by Park and co-workers. Further selective epoxidation of ent-1 leads to aquilanol B (2) in good yield. Finally, various structurally distinct highly oxidized eleven-membered cyclic scaffolds were reached in a selective manner, all originated from common intermediate (E)-allylic alcohol 12a,b, upon the action of specific acidic reagent.