Ligand‐Controlled Chemoselectivity in the Rhodium‐Catalyzed Synthesis of Pentafulvenes via (2 + 2 + 1) Alkyne Cyclotrimerization

Español-Sánchez, Belinda (Universidad de Zaragoza) ; Moradell, Jesús ; Galiana-Cameo, María ; Barrenas, Eduardo ; Pérez-Torrente, Jesús J. (Universidad de Zaragoza) ; Passarelli, Vincenzo ; Castarlenas, Ricardo

Resumen: 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.

Idioma: Inglés

DOI: 10.1002/anie.202507424

Año: 2025

Publicado en: Angewandte Chemie (International ed.) (2025), e202507424 ([6 pp.)
ISSN: 1433-7851

Financiación: info:eu-repo/grantAgreement/ES/DGA/E42-23R
Financiación: info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2022-137208NB-I00

Tipo y forma: Congress (Published version)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)