RT Journal Article
T1 Bis-CF3-bipyridine ligands for the Iridium-Catalyzed Borylation of N-Methylamides
A1 Marcos-Atanes, Daniel
A1 Jiménez-Osés, Gonzalo
A1 Mascareñas Cid, José Luis
K1 C−H activation
K1 Iridium catalysis
K1 Borylation
K1 Methylamides
K1 Bipyridine
AB Bipyridine and phenanthroline are well-established neutral ligands for promoting iridium-catalyzed borylations of aromatic C–H bonds. However, their use with aliphatic substrates is almost uncharted. Herein we demonstrate that introducing CF substituents at the 5- and 5′-positions of bipyridine generates ligands that enable an efficient and regioselective iridium-catalyzed borylation of the methyl group in a broad variety of methylamides. The reaction shows broad functional group tolerance and exhibits remarkable selectivity, offering a powerful approach for the borylation of challenging aliphatic C–H bonds. Mechanistic investigations, including computational analysis, suggest that the accelerating effect of the ligand is likely associated with the formation of non-covalent dispersion interactions between the carbonyl amide of the substrates and the trifluoromethylated pyridine rings of the ligand.
PB American Chemical Society
YR 2025
FD 2025-04
LK https://hdl.handle.net/10347/43305
UL https://hdl.handle.net/10347/43305
LA eng
NO Marcos-Atanes, D., Jiménez-Osés, G., & Mascareñas, J. L. (2025). Bis-CF3-bipyridine Ligands for the Iridium-Catalyzed Borylation of N-Methylamides. "ACS Catalysis", 15(9), 7112-7120. https://doi.org/10.1021/acscatal.5c00933
NO This work has received financial support from the Spanish Government (MCIN) through projects PID2022-137318OB-I00 and the grant IHRC22-00009 from the MCIN/ISCIII and the European Union Next Generation EU/PRTR (to J.L.M), and PID2021-125946OB-I00, CEX2021-001136-S (to G.J.O). We thank the Conselleria de Cultura, Educacion e Ordenacion Universitaria (Grant ED431C 2021/25, Grant ED431G 2023/03 and Centro de investigacio\u0301n do Sistema universitario de Galicia accreditation 2023-2027) and the European Union (European Regional Development Fund-ERDF corresponding to the multiannual financial framework 2014-2020). D.M. thanks MECD for a FPU fellowship (FPU18/04495). The Orfeo-Cinqa network (RED2022-134287-T) is also acknowledged. All calculations were carried out at the Centro de Supercomputacion de Galicia (CESGA). The authors thank Dr. M. Marcos and Dr. N. Atanes from CACTI (Universidade de Vigo) for their excellent technical assistance and essential contributions to the kinetic studies and the characterization of products. This work is dedicated to the memory of our beloved PhD student and friend Alejandro Gutierrez-Gonzalez
DS Minerva
RD 24 abr 2026