Joyce, Liam M.Drew, Melanie A.Tague, Andrew J.Thaima, ThanaphatGouranourimi, AliAriafard, AlirezaPyne, Stephen G.Hyland, Christopher J.T.2025-12-162025-12-160947-6539PubMed:34971450ORCID:/0000-0003-2383-6380/work/198195213https://hdl.handle.net/1885/733795524Thermally induced cycloisomerization reactions of 1,6-allenynes gives α-methylene-γ-lactams via intramolecular Alder-ene reactions. The mechanism is supported by computational and deuterium labelling studies. This thermal, non-radical method enables the discovery of a hitherto unknown route that proceeds via a divergent mechanism distinct from the previous [2+2] cycloisomerization manifold.The authors thank the Australian Research Council (grant number DP180101332) for the generous funding for this research. L. M. J. thanks the University of Wollongong for a PhD scholarship. The authors also acknowledge the Australian National Computational Infrastructure and the University of Tasmania for the generous allocation of computing time. The authors thank the Australian Research Council (grant number DP180101332) for the generous funding for this research. L. M. J. thanks the University of Wollongong for a PhD scholarship. The authors also acknowledge the Australian National Computational Infrastructure and the University of Tasmania for the generous allocation of computing time.5enPublisher Copyright: © 2021 Wiley-VCH GmbH.1,6-allenyneAlder-enecomputationscycloisomerizationlactam2021-12-2110.1002/chem.20210402285123908278