Low?Temperature Intramolecular [4+2] Cycloaddition of Allenes with Arenes for the Synthesis of Diene Ligands

The intramolecular [4+2] cycloaddition between arenes and allenes first reported by Himbert gives rapid access to rigid polycyclic scaffolds. Herein, we report a one-pot oxyalkynylation/cycloaddition reaction proceeding under mild conditions (23–90 °C) providing complex architectures with high efficiency, atom step economy. bicyclo[2.2.2]octadiene products were obtained wide variety of useful functional groups successfully applied as chiral ligands for metal catalysis. Computational studies gave rationalization the low activation energy based on counter-intuitive favorable dispersive interactions in transition state.