Construction of Cyclobutane‐Centered Tricyclic Caged Skeleton through a [5,5]‐Rearrangement Triggered Cascade

In this report, we describe the combination of [5,5]‐rearrangement‐triggered dearomatization recently developed in our laboratory with an intramolecular formal [2+2]‐cycloaddition for constructing an intriguing polysubstituted tricyclo[4.2.1.03,8]nonane derivatives. The synthesis features the use of simple and readily available three distinct starting materials including aryl sulfoxides, allyl nitriles, and certain nucleophiles or dienes which directly enriches the diversity of target molecules. This study provides an entirely new protocol for the synthesis of cyclobutane‐centered tricyclic caged skeleton.