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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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Publication details

The article was received on 08 Oct 2019, accepted on 16 Nov 2019 and first published on 18 Nov 2019


Article type: Edge Article
DOI: 10.1039/C9SC05076K
Chem. Sci., 2020, Advance Article
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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

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

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