Cu(OTf)2‐mediated cross‐coupling of nitriles and N‐heterocycles with arylboronic acids to generate nitrilium and pyridinium products

Bell, N. L. et al. (2021) Cu(OTf)2‐mediated cross‐coupling of nitriles and N‐heterocycles with arylboronic acids to generate nitrilium and pyridinium products. Angewandte Chemie (International Edition), 60(14), pp. 7935-7940. (doi: 10.1002/anie.202016811) (PMID:33449408) (PMCID:PMC8048606)

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Abstract

Metal-catalyzed C–N cross-coupling generally forms C−N bonds by reductive elimination from metal complexes bearing covalent C- and N-ligands. We have identified a Cu-mediated C–N cross-coupling that uses a dative N-ligand in the bond-forming event, which, in contrast to conventional methods, generates reactive cationic products. Mechanistic studies suggest the process operates via transmetalation of an aryl organoboron to a CuII complex bearing neutral N-ligands, such as nitriles or N-heterocycles. Subsequent generation of a putative CuIII complex enables the oxidative C–N coupling to take place, delivering nitrilium intermediates and pyridinium products. The reaction is general for a range of N(sp) and N(sp2) precursors and can be applied to drug synthesis and late-stage N-arylation, and the limitations in the methodology are mechanistically evidenced.

Item Type:Articles
Additional Information:N.L.B. thanks the EPSRC for postdoctoral funding (EP/R025754/1). C.X. and J.W.B.F. thank the Leverhulme Trust for postdoctoral funding (RPG-2015-308; RPG-2018-362). J.C.V. thanks GlaxoSmithKline for a PhD studentship. J.B. thanks AstraZeneca for a PhD studentship. S.B. thanks the University of St Andrews for a PhD studentship.
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Bell, Dr Nicola
Authors: Bell, N. L., Xu, C., Fyfe, J. W.B., Vantourout, J. C., Brals, J., Chabbra, S., Bode, B. E., Cordes, D. B., Slawin, A. M.Z., McGuire, T. M., and Watson, A. J.B.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Angewandte Chemie (International Edition)
Publisher:Wiley
ISSN:1433-7851
ISSN (Online):1521-3773
Published Online:15 January 2021
Copyright Holders:Copyright © 2021 The Authors
First Published:First published in Angewandte Chemie (International Edition) 60(14): 7935-7940
Publisher Policy:Reproduced under a Creative Commons License

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