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How intramolecular hydrogen bonding (IHB) controls the C-ON bond homolysis in alkoxyamines Full article

Journal Organic and Biomolecular Chemistry
ISSN: 1477-0520 , E-ISSN: 1477-0539
Output data Year: 2017, Volume: 15, Number: 39, Pages: 8425-8439 Pages count : 15 DOI: 10.1039/c7ob02223a
Authors Audran Gerard 1 , Bikanga Raphael 2 , Bremond Paul 1 , Edeleva Mariya 3 , Joly Jean-Patrick 1 , Marque Sylvain R.A. 1,3 , Nkolo Paulin 1 , Roubaud Valerie 1
Affiliations
1 (Данные Web of science) Aix Marseille Univ, CNRS, ICR, UMR 7273, Case 551,Ave Escadrille Normandie Niemen, F-13397 Marseille 20, France
2 (Данные Web of science) Univ Sci & Tech Masuku, Lab Subst Nat & Synth Organomet, BP 943, Franceville, Gabon
3 (Данные Web of science) NN Vorozhtsov Novosibirsk Inst Organ Chem SB RAS, Pr Lavrentjeva 9, Novosibirsk 630090, Russia

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 R-3, 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.
Cite: Audran G. , Bikanga R. , Bremond P. , Edeleva M. , Joly J-P. , Marque S.R.A. , Nkolo P. , Roubaud V.
How intramolecular hydrogen bonding (IHB) controls the C-ON bond homolysis in alkoxyamines
Organic and Biomolecular Chemistry. 2017. V.15. N39. P.8425-8439. DOI: 10.1039/c7ob02223a WOS Scopus РИНЦ
Files: Full text from publisher
Identifiers:
Web of science WOS:000412827300021
Scopus 2-s2.0-85031329472
Elibrary 31064811
OpenAlex W2760107856
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