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Chemically triggered C-ON bond homolysis in alkoxyamines. Part 7. Remote polar effect

Abstract : In a recent work (Org. Lett. 2012, 14, 358-361), we showed that the activation by benzylation of alkoxyamine 1 (diethyl (1-(tert-butyl(1-(pyridin-4-yl)ethoxy)amino)-2,2-dimethylpropyl)phosphon ate) afforded a surprisingly large C-ON bond homolysis rate constant k(d). Taking advantage of the easy preparation of para-X-benzyl-activated alkoxyamines 2 and of the presence of a shielding methylene group between the two aromatic moieties, we investigated the long range (10 bonds between the X group and the C-ON bond) polar effect for X=H, F, OMe, CN, NO2, NMe2, +NHMe2,Br-. It was observed that the effect was weak (4-fold) and mainly due to the zwiterionic mesomeric forms generated by the presence of group X on the para position, i.e. k(d) increased for CN and NO2 and decreased for OMe, NMe2 and +NMe2H,Br-. DFT calculations at the B3LYP/6-31G(d,p) level were performed to determine orbital interactions (natural bond orbital (NBO) analysis), Mulliken and NBO charges which support the reactivity described. Copyright (c) 2014 John Wiley & Sons, Ltd.
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Submitted on : Monday, December 12, 2016 - 6:49:29 PM
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Gérard Audran, Matisse Bim Batsiandzy Ibanou, Paul Brémond, Sylvain R.A. Marque, Germain Obame, et al.. Chemically triggered C-ON bond homolysis in alkoxyamines. Part 7. Remote polar effect. Journal of Physical Organic Chemistry, Wiley, 2014, 27 (5), pp.387--391. ⟨10.1002/poc.3275⟩. ⟨hal-01415169⟩

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