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Cu(OTf)2-Mediated Ionizing Cross-Coupling of N(sp) and N(sp2) with Arylboronic Acids

preprint
submitted on 17.12.2020, 12:44 and posted on 18.12.2020, 13:45 by Allan Watson, Nicola Bell, Chao Xu, James Fyfe, Julien Vantourout, Jeremy Brals, sonia chabbra, Bela Bode, David Cordes, Alexandra Slawin, Thomas McGuire
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.

Funding

Chemoselective cross-coupling via control of anion metathesis at Pd(II)

Engineering and Physical Sciences Research Council

Find out more...

RPG-2015-308

RPG-2018-362

History

Email Address of Submitting Author

aw260@st-andrews.ac.uk

Institution

University of St Andrews

Country

United Kingdom

ORCID For Submitting Author

0000-0002-1582-4286

Declaration of Conflict of Interest

No conflicts of interest

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