Study of the mechanism of copper-activated NHC–R and NHC=O coupling under the conditions of the Chan–Evans–Lam reaction system

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Abstract

In this work, the phenomena of copper-induced formation of NHC-R and NHC=O particles in the Chan–Evans–Lam arylation reaction system of aniline are discussed for the first time. The considered combinations between NHC and arylboronic acid residues have been demonstrated using 5 different arylboronic acids and three Cu/NHC complexes. It is also shown that the formation of the azolone NHC=O is due to copper-mediated oxygen transfer from the atmosphere to the carbene center of the NHC. Using a set of experimental physicochemical methods of analysis, as well as with the help and methods of quantum chemistry, it is shown for the first time that the degradation pathway of Cu/NHC complexes through the formation of NHC–R is controlled kinetically, and through the formation of NHC=O - thermodynamically, which makes a significant contribution to the understanding of the observed phenomena.

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About the authors

A. S. Galushko

Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences

Author for correspondence.
Email: galushkoas@ioc.ac.ru
Russian Federation, 119991 Moscow

V. A. Skuratovich

Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences

Email: galushkoas@ioc.ac.ru
Russian Federation, 119991 Moscow

M. V. Grudova

Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences

Email: galushkoas@ioc.ac.ru
Russian Federation, 119991 Moscow

V. V. Ilyushenkova

Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences

Email: galushkoas@ioc.ac.ru
Russian Federation, 119991 Moscow

R. R. Shaydullin

Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences

Email: galushkoas@ioc.ac.ru
Russian Federation, 119991 Moscow

D. O. Prima

Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences

Email: galushkoas@ioc.ac.ru
Russian Federation, 119991 Moscow

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Supplementary files

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2. Fig. 1. Known pathways for the formation of NHC–R and NHC=O particles in catalytic systems based on nickel and palladium NHC complexes (a) [22, 26]; in this work, we investigated the mechanism of formation of NHC–R and NHC=O particles in the Chan–Evans–Lam reaction from Cu/NHC complexes (b).

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3. Scheme 1. Scheme of the reaction for the arylation of aniline, five arylboronic acids 1–5 and four M/NHC complexes used in the study.

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4. Fig. 2. Proposed mechanism of formation of NHC–Ar and NHC=O particles in Cu/NHC systems with arylboronic acids under Chan–Evans–Lam reaction conditions. TS – transition state, NP – nanoparticles (a); potential energy surfaces for the formation of BIMe–Ph and BIMe=O products from a single precursor (b).

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5. Fig. 3. STEM images of nanoparticles formed in the reaction system with arylboronic acid 5 (the sample was taken 5 h after the start of the reaction) (a)–(d); ESI-HRMS spectra confirming the presence of the NHC–R coupling product in the presence of atmospheric oxygen (d) and its absence in an oxygen-free environment (e).

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6. Appendix
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