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Issue 39, 2017
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How intramolecular hydrogen bonding (IHB) controls the C–ON bond homolysis in alkoxyamines

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Abstract

Recent amazing results (Nkolo et al., Org. Biomol. Chem., 2017, 6167) on the effect of solvents and polarity on the C–ON bond homolysis rate constants kd of alkoxyamine R1R2NOR3 led us to re-investigate the antagonistic effect of intramolecular hydrogen-bonding (IHB) on kd. Here, IHB is investigated both in the nitroxyl fragment R1R2NO and in the alkyl fragment R3, as well as between fragments, that is, the donating group on the alkyl fragment and the accepting group on the nitroxyl fragment, and conversely. It appears that IHB between fragments (inter IHB) strikingly decreases the homolysis rate constant kd, whereas IHB within the fragment (intra IHB) moderately increases kd. For one alkoxyamine, the simultaneous occurrence of IHB within the nitroxyl fragment and between fragments is reported. The protonation effect is weaker in the presence than in the absence of IHB. A moderate solvent effect is also observed.

Graphical abstract: How intramolecular hydrogen bonding (IHB) controls the C–ON bond homolysis in alkoxyamines

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Publication details

The article was received on 04 Sep 2017, accepted on 14 Sep 2017 and first published on 27 Sep 2017


Article type: Paper
DOI: 10.1039/C7OB02223A
Org. Biomol. Chem., 2017,15, 8425-8439
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    How intramolecular hydrogen bonding (IHB) controls the C–ON bond homolysis in alkoxyamines

    G. Audran, R. Bikanga, P. Brémond, M. Edeleva, J. Joly, S. R. A. Marque, P. Nkolo and V. Roubaud, Org. Biomol. Chem., 2017, 15, 8425
    DOI: 10.1039/C7OB02223A

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