To illustrate the utilities of this method, we conducted this reaction on a preparative scale with silyl enol ether 1w and BCB 2a, which afforded the cycloadduct 3w in 91% yield (770 mg). Both the ketone and tertiary alcohol moieties in 3w provided handles for further synthetic elaborations to procure a wide array of new bicyclo[2.1.1]hexanes. Specifically, subjecting bicycle 3w to the Wittig reaction condition led to olefin 6. After deprotection of the silyl group, the free alcohol 7 have been proved versatile for various transformations, including the dehydration to olefin 8 by treatment with Burgess reagent and fluorination to 9 in the presence of DAST reagent. Furthermore, isonitrile 10 would be readily obtained using Shenvi's methodology. All of derivatizations above further extended the attainability of new bicyclo[2.1.1]hexanes using this developed manifold.