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 methylati...

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Bibliographic Details
Published in:Organic letters 2012-01, Vol.14 (1), p.358-361
Main Authors: Brémond, Paul, Koïta, Abdoulaye, Marque, Sylvain R. A, Pesce, Vincent, Roubaud, Valérie, Siri, Didier
Format: Article
Language:English
Subjects:
Chemical Sciences
or physical chemistry
Theoretical and
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Summary: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.
ISSN:1523-7060
1523-7052
DOI:10.1021/ol2031075