PMID: 11312941Apr 21, 2001Paper

Factors influencing the C-O bond homolysis of alkoxyamines: effects of H-bonding and polar substituents

The Journal of Organic Chemistry
S MarqueA Studer

Abstract

The synthesis of various new trialkylhydroxylamines is described. The rate constant of the C-O bond cleavage of these new alkoxyamines has been measured. For example, C-O bond homolysis rates in a series of para-substituted TEMPO-styryl compounds TEMPO-CH(CH3)C6H5X 1a (p-MeO), 1b (p-Me), 1d (p-H), 1e (p-Br), and 1f (p-MeO2C) are presented. Furthermore, rate constants for the C-O bond cleavage of alpha-heteroaryl-substituted secondary alkoxyamines are discussed. A correlation by which the rate constant for the C-O bond cleavage of TEMPO-derived alkoxyamines can be predicted from the C-H BDEs of the corresponding alkanes is presented. Solvent effects as well as the effect of camphorsulfonic acid on the rate of the C-O bond homolysis are discussed. Finally, EPR and kinetic evidence show that alkoxyamines derived from nitroxides which are capable of intramolecular H-bonding undergo C-O bond cleavage faster than the corresponding non-H-bond-forming analogues.

Citations

Apr 5, 2005·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Armido Studer, Tobias Schulte
Feb 19, 2011·Chemical Communications : Chem Comm·Maike BeckerArmido Studer
Aug 10, 2013·Biotechnology and Bioengineering·Kirill RachinskiyJochen Büchs
Sep 16, 2016·Journal of the American Chemical Society·Ming YanPhil S Baran
Feb 8, 2006·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Anouk Gaudel-SiriPaul Tordo
Jun 18, 2004·Organic Letters·Rebecca BraslauJennifer Gewandter
Mar 16, 2016·Organic & Biomolecular Chemistry·Gérard AudranToshihide Yamasaki
May 13, 2014·Chemical Communications : Chem Comm·Gérard AudranSylvain R A Marque
Sep 6, 2017·Organic & Biomolecular Chemistry·Nadia GruberPierluigi Stipa
Jan 18, 2008·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Denis BertinGregory Trappo
Oct 11, 2008·Angewandte Chemie·Joyram GuinArmido Studer
Jul 1, 2009·Macromolecular Rapid Communications·Marion K Brinks, Armido Studer
Aug 5, 2010·Angewandte Chemie·Birte SchulteLuisa De Cola
May 4, 2011·Angewandte Chemie·Ludger Tebben, Armido Studer
May 26, 2020·Macromolecular Rapid Communications·Gianni CavalloJean-François Lutz
Feb 23, 2012·Macromolecular Rapid Communications·Simon HarrissonJulien Nicolas
Sep 28, 2017·Organic & Biomolecular Chemistry·Gérard AudranValérie Roubaud
Nov 20, 2016·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Gérard AudranStéphane Viel
May 18, 2010·The Journal of Physical Chemistry. C, Nanomaterials and Interfaces·Chittreeya TansakulRebecca Braslau
Jun 25, 2021·Chemical Science·Olga GuselnikovaPavel Postnikov
May 3, 2012·Journal of the American Chemical Society·Muhammad SajidGerhard Erker
Sep 4, 2010·The Journal of Physical Chemistry. a·Jennifer L HodgsonMichelle L Coote
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Sep 28, 2013·The Journal of Organic Chemistry·Paul BrémondStéphane Viel
Jul 17, 2013·The Journal of Organic Chemistry·Gérard AudranGermain Obame
Jun 7, 2007·Organic Letters·Veronica Mugnaini, Marco Lucarini
Sep 26, 2006·The Journal of Organic Chemistry·David BardelangPaul Tordo

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