Hari, Durga PrasadPisella, GuillaumeWodrich, Matthew D.Tsymbal, Artem V.Tirani, Farzaneh FadaeiScopelliti, RosarioWaser, Jerome2021-03-212021-03-212021-03-212020-11-2010.1002/anie.202012299https://infoscience.epfl.ch/handle/20.500.14299/176056The 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) and providing complex polycyclic architectures with high efficiency, and atom and step economy. The bicyclo[2.2.2]octadiene products were obtained with a wide variety of useful functional groups and were successfully applied as chiral ligands for metal catalysis. Computational studies gave a first rationalization of the low activation energy for the cycloaddition based on counter‐intuitive favorable dispersive interactions in the transition state.text::journal::journal article::research article