Intramolecular Diels-Alder Reaction of Cyclopropenyl Vinylarenes: Access to Benzonorcarane Derivatives

Intramolecular Diels-Alder vinylarene reaction (IMDAV) is a [4 + 2] cycloaddition that employs styrene derivatives as conjugated dienes, whose poor reactivity arises from the required loss of aromaticity, which is recovered by a subsequent [1,3]-H shift. Herein, we describe the use of cyclopropene as a dienophile, harnessing its strain energy to drive the IMDAV reaction. Benzonorcarane scaffolds form in good yields, excellent stereoselectivity, and broad functional tolerance. Theoretical calculations and NMR studies have revealed significant mechanistic insights.