Bell, Nicola L.;
Xu, Chao;
Fyfe, James W. B.;
Vantourout, Julien C.;
Brals, Jeremy;
Chabbra, Sonia;
Bode, Bela E.;
Cordes, David B.;
Slawin, Alexandra M. Z.;
McGuire, Thomas M.;
Watson, Allan J. B.
Cu(OTf)2‐Mediated Cross‐Coupling of Nitriles and N‐Heterocycles with Arylboronic Acids to Generate Nitrilium and Pyridinium Products**
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Media type:
E-Article
Title:
Cu(OTf)2‐Mediated Cross‐Coupling of Nitriles and N‐Heterocycles with Arylboronic Acids to Generate Nitrilium and Pyridinium Products**
Contributor:
Bell, Nicola L.;
Xu, Chao;
Fyfe, James W. B.;
Vantourout, Julien C.;
Brals, Jeremy;
Chabbra, Sonia;
Bode, Bela E.;
Cordes, David B.;
Slawin, Alexandra M. Z.;
McGuire, Thomas M.;
Watson, Allan J. B.
Published:
Wiley, 2021
Published in:
Angewandte Chemie International Edition, 60 (2021) 14, Seite 7935-7940
Language:
English
DOI:
10.1002/anie.202016811
ISSN:
1433-7851;
1521-3773
Origination:
Footnote:
Description:
AbstractMetal‐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 CuIIcomplex bearing neutral N‐ligands, such as nitriles or N‐heterocycles. Subsequent generation of a putative CuIIIcomplex 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.