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

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 k_d of alkoxyamine R₁R₂NOR₃ led us to re-investigate the antagonistic effect of intramolecular hydrogen-bonding (IHB) on k_d. 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 k_d, whereas IHB within the fragment (intra IHB) moderately increases k_d. 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.