Chemically triggered C-ON bond homolysis of alkoxyamines. Quaternization of the alkyl fragment.

The C-ON bond homolysis in alkoxyamine 2a can be chemically triggered by the protonation of the 4-pyridylalkyl fragment. The resulting 15-fold increase in k(d) (Chem. Commun. 2011, 47, 4291-4293) was investigated experimentally and theoretically by quaternization of the pyridyl moiety using methylating (MeOTs), acylating (AcCl), and benzylating (PhCH(2)Br) agents as well as by oxidation of the pyridyl moiety into N-oxide and by the formation of a dative bond with BH(3) as a Lewis acid.