Chemically Triggered C-ON Bond Homolysis of Alkoxyamines. Quaternization of the Alkyl Fragment

Paul Brémond (1) , Abdoulaye Koita (2) , Sylvain R.A. Marque (1) , Vincent Pesce (2) , Valérie Roubaud (1) , Didier Siri (1)

1 ICR - Institut de Chimie Radicalaire
2 LCP - Laboratoire Chimie Provence

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 (PhCH2Br) agents as well as by oxidation of the pyridyl moiety into N-oxide and by the formation of a dative bond with BH3 as a Lewis acid.

Domaines: Chimie théorique et/ou physique

Paul Brémond, Abdoulaye Koita, Sylvain R.A. Marque, Vincent Pesce, Valérie Roubaud, et al.. Chemically Triggered C-ON Bond Homolysis of Alkoxyamines. Quaternization of the Alkyl Fragment. Organic Letters, 2012, 14 (1), pp.358--361. ⟨10.1021/ol2031075⟩. ⟨hal-01415186⟩