the desired transformation (Scheme 5). Among them Sc(OTf)3 gave the cleanest reaction profile, providing access to the enantiomer of natural aquilanol A (1) in 74% yield, presumable due to its ability of concomitant activation of epoxide and complexation of the allylic hydroxyl group, thus bringing in proximity the reacting components. Furthermore, m-CPBA oxidation of ent-1, led exclusively to natural aquilanol B (2) in 78% yield, with the disubstituted double bond Δ being the only reactive site. The spectroscopic and physical data were in excellent agreement with the reported ones by the isolation group. In addition, having ensure a rapid access to the respective (E)allylic alcohol, in the form of two stable conformers 12a,b (see Scheme 2), we were curious whether analogues of the natural product could be derived from. Against our expectations, treatment with various types of acids did not cause an analogous intramolecular epoxide opening, instead provided access to several structurally distinct products, often with admirable chemoselectivity, a fact that renders alcohols 12a,b a valuable common intermediate to a versatile array of highly oxidized carbocyclic motifs (Scheme 6). In particular, treatment of 12a,b with typical Lewis acids such as SnCl4, or TiCl4, afforded exomethylene allylic alcohol 15 as the major product (please see supporting information Scheme S1 for mechanistic interpretation). On the other hand, BF3•OEt2 resulted in the formation of a pinacol type rearrangement product, ketone 16. When alcohols 12a,b were subjected to the action of a Brønsted acid, regardless its strength, a known rearrangement took place, triggered by nucleophilic attack of the nearby disubstituted double bond, to provide cyclopropyl triol 17. 15 Scheme 6. Highly oxidized carbocyclic scaffolds from treatment of (E)-allylic alcohols 12a,b with various acids.