In order to evaluate the synthetic versatility and utility of the obtained BCO diketones, their modifications were then investigated (Scheme 4). We focused on BCO 4aa, containing a naphthyl group on the carbonyl function. In this case, chemoselective functionalization is facilitated as only the carbonyl group on the bicyclooctane scaffold is enolizable. Accordingly, 4aa was smoothly converted into enol triflate 5 in 72% yield under kinetic-controlled conditions. This compound was the starting material for a series of subsequent transformations. Styrene 6 and alkene 7 were both accessed in good yields through a Suzuki cross coupling reaction and, respectively, a Pd 0 -catalyzed reduction with Bu3SnH. A Stille coupling allowed to synthesize diene 8. Refluxing the latter with DMAD followed by oxidation with DDQ permitted to forge benzene-fused product 9 quantitatively. The completely reduced, saturated skeleton of bicycle [4.1.1]octane could be accessed by catalytic hydrogenation of 10 in the presence on Li2CO3. Unfortunately, a yield higher than 50% could be obtained because of its sensitivity to overreduction. In summary, the first formal (4π+2σ) cycloaddition of BCB ketones with dienol silyl ethers has been disclosed. The reaction occured under mild conditions, using commercially available Al(OTf)3 as a Lewis acid catalyst, and represents a convenient modular method for the synthesis of uncommon biyclo [4.1.1]octane carbocycles. The latter could be generally obtained in good to very good yields, with a wide tolerance of substituents on both the substrate and the diene, including alkyl as well as electron-rich and -poor aryl groups. The obtained products were available for an array of further transformations, giving access to BCO derivatives with different fractions of Csp 3 . As the importance of biyclo [4.1.1]octanes has started emerging in the search for new bridged cycloalkanes with bioisosteric properties, we believe that our protocol for the expedient preparation of these intriguing frameworks will contribute to facilitate and accelerate research on them.