Bicyclo[2.1.1]hexanes via Intramolecular Formal (3+2)‐Cycloaddition

We report a synthesis of bicyclo[2.1.1]hexanes via an intramolecular formal (3+2) cycloaddition of allylated cyclopropanes bearing a 4‐nitrobenzimine substituent. Both activated and unactivated alkenes are tolerated in the transformation. The bicyclic imine products are prone to photo‐induced ring opening, allowing for the epimerization of C5‐stereogenic compounds.