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

Belinda Español‐Sánchez; Jesús Moradell; María Galiana‐Cameo; Eduardo Barrenas; Jesús J. Pérez‐Torrente; Vincenzo Passarelli; Ricardo Castarlenas

doi:10.1002/anie.202507424

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

B Belinda Español‐Sánchez (Instituto de Síntesis Química y Catálisis Homogénea (ISQCH)‐Departamento de Química Inorgánica CSIC‐Universidad de Zaragoza C/Pedro Cerbuna 12, CP Zaragoza 50009 Spain) J Jesús Moradell (Instituto de Síntesis Química y Catálisis Homogénea (ISQCH)‐Departamento de Química Inorgánica CSIC‐Universidad de Zaragoza C/Pedro Cerbuna 12, CP Zaragoza 50009 Spain) M María Galiana‐Cameo (Instituto de Síntesis Química y Catálisis Homogénea (ISQCH)‐Departamento de Química Inorgánica CSIC‐Universidad de Zaragoza C/Pedro Cerbuna 12, CP Zaragoza 50009 Spain) E Eduardo Barrenas (Instituto de Síntesis Química y Catálisis Homogénea (ISQCH)‐Departamento de Química Inorgánica CSIC‐Universidad de Zaragoza C/Pedro Cerbuna 12, CP Zaragoza 50009 Spain) J Jesús J. Pérez‐Torrente (Instituto de Síntesis Química y Catálisis Homogénea (ISQCH)‐Departamento de Química Inorgánica CSIC‐Universidad de Zaragoza C/Pedro Cerbuna 12, CP Zaragoza 50009 Spain) V Vincenzo Passarelli (Instituto de Síntesis Química y Catálisis Homogénea (ISQCH)‐Departamento de Química Inorgánica CSIC‐Universidad de Zaragoza C/Pedro Cerbuna 12, CP Zaragoza 50009 Spain) R Ricardo Castarlenas (Instituto de Síntesis Química y Catálisis Homogénea (ISQCH)‐Departamento de Química Inorgánica CSIC‐Universidad de Zaragoza C/Pedro Cerbuna 12, CP Zaragoza 50009 Spain)

Abstract

Abstract 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.

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Article Details

Journal Angewandte Chemie International Edition

Volume / Issue Vol. 64, Issue 34

Published August 18, 2025

DOI 10.1002/anie.202507424

ISSN 1433-7851

Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences