title: C-ON Bond Homolysis of Alkoxyamines, Part 11: Activation of the Nitroxyl Fragment.
abstract: A few years ago, Bagryanskaya and colleagues (J. Org. Chem. 2011) showed that protonation of the nitroxyl fragment deactivated the alkoxyamine C-ON bond. Conversely, our group showed that protonation (Chem. Commun. 2011), as well as other chemical reactions such as oxidation or amine quaternization (Org. Lett. 2012), of the pyridyl moiety carried by the alkyl fragment was suitable to activate the homolysis of the C-ON bond. To pursue our goal of applying alkoxyamines as theranostic agents (Org. Biomol. Chem. 2014 and Mol. Pharmaceutics 2014) by activation of the C-ON bond homolysis, we turned our interest to the chemical activation of the nitroxyl fragment by oxidation/reduction of selected functions. Conversion of a hydroxyl group located close to the nitroxyl moiety successively into aldehyde, then acid, and eventually into ester, led to a successive decrease in kd.
authors.affiliation: Aix Marseille Université, CNRS, ICR, UMR 7273 , 13397 Marseille Cedex 20, France.
authors.forename: Gérard
authors.initials: G
authors.lastname: Audran
authors.affiliation: Aix Marseille Université, CNRS, ICR, UMR 7273 , 13397 Marseille Cedex 20, France.
authors.forename: Paul
authors.initials: P
authors.lastname: Brémond
authors.affiliation: Aix Marseille Université, CNRS, ICR, UMR 7273 , 13397 Marseille Cedex 20, France.|N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS , Pr. Lavrentjeva 9, 630090 Novosibirsk, Russia.
authors.forename: Sylvain R A
authors.initials: SR
authors.lastname: Marque
authors.affiliation: Aix Marseille Université, CNRS, ICR, UMR 7273 , 13397 Marseille Cedex 20, France.
authors.forename: Toshihide
authors.initials: T
authors.lastname: Yamasaki