Cu(OTf) 2 ‐Mediated Cross‐Coupling of Nitriles and N‐Heterocycles with Arylboronic Acids to Generate Nitrilium and Pyridinium Products**

Autor: Nicola L. Bell, Thomas M. McGuire, Sonia Chabbra, Alexandra M. Z. Slawin, James W. B. Fyfe, David B. Cordes, Allan J. B. Watson, Chao Xu, Julien C. Vantourout, Bela E. Bode, Jeremy Brals
Přispěvatelé: The Leverhulme Trust, EPSRC, University of St Andrews. Sir James Mackenzie Institute for Early Diagnosis, University of St Andrews. School of Chemistry, University of St Andrews. EaSTCHEM, University of St Andrews. Biomedical Sciences Research Complex, University of St Andrews. Centre of Magnetic Resonance
Rok vydání: 2021
Předmět:
Zdroj: Angewandte Chemie International Edition. 60:7935-7940
ISSN: 1521-3773
1433-7851
Popis: Funding: Leverhulme Trust (Grant Number(s): RPG-2015-308), Leverhulme Trust (Grant Number(s): RPG-2018-362), Engineering and Physical Sciences Research Council (Grant Number(s): EP/R025754/1). 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 Cu(II) complex bearing neutral N‐ligands, such as nitriles or N‐heterocycles. Subsequent generation of a putative Cu(III) 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. Publisher PDF
Databáze: OpenAIRE
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