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Issue 2, 2020
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Unravelling the mechanism of cobalt-catalysed remote C–H nitration of 8-aminoquinolinamides and expansion of substrate scope towards 1-naphthylpicolinamide

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Abstract

Previously, an unexpected Co-catalysed remote C–H nitration of 8-aminoquinolinamide compounds was developed. This report provided a novel reactivity for Co which was assumed to proceed through the mechanistic pathway already known for analogous Cu-catalysed remote couplings of the same substrates. In order to shed light into this intriguing, and previously unobserved reactivity for Co, a thorough computational study has now been performed, which has allowed for a full understanding of the operative mechanism. This study demonstrates that the Co-catalysed remote coupling does not occur through the previously proposed Single Electron Transfer (SET) mechanism, but actually operates through a high-spin induced remote radical coupling mechanism, through a key intermediate with significant proportion of spin density at the 5- and 7-positions of the aminoquinoline ring. Additionally, new experimental data provides expansion of the synthetic utility of the original nitration procedure towards 1-naphthylpicolinamide which unexpectedly appears to operate via a subtly different mechanism despite having a similar chelate environment.

Graphical abstract: Unravelling the mechanism of cobalt-catalysed remote C–H nitration of 8-aminoquinolinamides and expansion of substrate scope towards 1-naphthylpicolinamide

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Article information


Submitted
08 Oct 2019
Accepted
16 Nov 2019
First published
18 Nov 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 534-542
Article type
Edge Article

Unravelling the mechanism of cobalt-catalysed remote C–H nitration of 8-aminoquinolinamides and expansion of substrate scope towards 1-naphthylpicolinamide

M. Chu, O. Planas, A. Company, X. Ribas, A. Hamilton and C. J. Whiteoak, Chem. Sci., 2020, 11, 534
DOI: 10.1039/C9SC05076K

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