162126 20251017144628.0 doi 10.1002/anie.202507424 sideral 144741 ART-2025-144741 eng Español-Sánchez, Belinda Universidad de Zaragoza Ligand‐Controlled Chemoselectivity in the Rhodium‐Catalyzed Synthesis of Pentafulvenes via (2 + 2 + 1) Alkyne Cyclotrimerization 2025 Access copy available to the general public Unrestricted The synthesis of pentafulvenes with varied substituents has been efficiently achieved using novel rhodium‐based catalysts via (2 + 2 + 1) alkyne cyclotrimerization. A rational design of the catalyst structure, including pyridonato, NHC, and CO ligands, ensures the alkyne chemoselectivity and prevents the formation of robust rhodium‐fulvene species. Furthermore, the judicious choice of acidity and steric properties of different alkynes enables the preparation of cross‐coupled fulvene derivatives. Stoichiometric and deuteration experiments, as well as DFT calculations, shed light on the reaction mechanism, showing that it includes an initial alkyne deprotonation, two successive alkyne insertions, cyclization, and protonolysis, the first insertion being the rate‐determining step. info:eu-repo/grantAgreement/ES/DGA/E42-23R info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00 info:eu-repo/grantAgreement/ES/MICINN/PID2022-137208NB-I00 info:eu-repo/semantics/openAccess by-nc https://creativecommons.org/licenses/by-nc/4.0/deed.es info:eu-repo/semantics/conferenceObject info:eu-repo/semantics/publishedVersion Moradell, Jesús Galiana-Cameo, María (orcid)0000-0002-2043-4864 Barrenas, Eduardo Pérez-Torrente, Jesús J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 Passarelli, Vincenzo (orcid)0000-0002-1735-6439 Castarlenas, Ricardo (orcid)0000-0003-4460-8678 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica (2025), e202507424 ([6 pp.) Angew. Chem. (Int. ed.) Angewandte Chemie (International ed.) 1433-7851 2206214 http://zaguan.unizar.es/record/162126/files/texto_completo.pdf Versión publicada 2756988 http://zaguan.unizar.es/record/162126/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:162126 articulos driver 2025-10-17-14:25:00 ARTICLE