RT Journal Article
T1 Ligand-Enabled Chemo- and Regioselective Ir(I)-Catalyzed Intermolecular Hydrocarbonation of Allenes: Access to Branched Products with All-Carbon Quaternary Centers
A1 Rey López, Alejandro
A1 Arribas Domingo, Andrés
A1 Mascareñas Cid, José Luis
A1 López García, Fernando José
K1 Allenes
K1 C─H activation
K1 Enantioselective
K1 Hydroarylation
K1 Iridium
AB An iridium complex featuring the perfluorinated bisphosphine ligand dFppe can catalyze intermolecular hydrocarbonation reactions of allenes with precise control over the selectivity to yield highly valuable branched products instead of the more common linear derivatives. Using N-substituted 3-carboxamide pyrroles as C─H donors, the reaction gives exclusively C-4 substituted products, while furan analogues yield C-2 substituted derivatives. β-Unsubstituted acrylamides can also be used as C─H sources to give chiral skipped dienes. The additions are equally efficient using monosubstituted and 1,1-disubstituted allenes, enabling the efficient formation of products bearing tertiary and all-carbon quaternary stereocenters. Moreover, a preliminary analysis with chiral bisphosphinite ligands confirms the feasibility of an enantioselective variant. Computational (DFT) studies provide relevant insights into this remarkable ligand-driven branched selectivity.
PB Wiley
SN 1433-7851
YR 2025
FD 2025-08-22
LK https://hdl.handle.net/10347/43382
UL https://hdl.handle.net/10347/43382
LA eng
NO Rey, A., Arribas, A., Mascareñas, J. L., & López, F. (2025). Ligand-Enabled Chemo- and Regioselective Ir(I)-Catalyzed Intermolecular Hydrocarbonation of Allenes: Access to Branched Products with All-Carbon Quaternary Centers. “Angewandte Chemie International Edition”, 64(40) https://doi.org/10.1002/anie.202512027
NO This work received financial support from the Spanish Government (Grants PID2020-118579GB-I00, PID2022-139318NB-I00, and PID2023-152054NB-I00 funded by MCIN/AEI/ 10.13039/501100011033, ORFEO-CINQA network RED2022-134287-T, Grant IHRC22-00009 funded by MCIN/ISCIII and by the “European Union Next Generation EU/PRTR”). All authors also thank the Xunta de Galicia (Grant ED431C 2021/25 and Grant ED431G 2023/03: Centro de Investigación do Sistema Universitario de Galicia accreditation 2023–2027) and the European Union (European Regional Development Fund-ERDF corresponding to the multiannual financial framework). All calculations were carried out at the Centro de Supercomputación de Galicia (CESGA). They also thank the Xunta de Galicia for the scholarship to A.R and Dr. Martin Calvelo for helpful discussions.
DS Minerva
RD 1 may 2026