Density functional and spectroscopic studies of nitrogen inversion in substituted dizocilpines

Aliev, Abil E., Sinclair, Alex J., Zhou, Shen, Wilden, John D., Caddick, Stephen, Kullmann, Dimitri M. and Rusakov, Dmitri A. (2009) Density functional and spectroscopic studies of nitrogen inversion in substituted dizocilpines. Journal of Physical Organic Chemistry, 22(6), pp. 607-612. ISSN (print) 0894-3230

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Abstract

While developing a synthesis towards tagged dizocilpine (MK-801) analogues, we observed highly restricted inversion of a nitrogen centre in a number hydroxylamines obtained as key intermediates. These compounds are shown to possess some of the structural elements which are expected to significantly hinder the nitrogen inversion, potentially leading to hydroxylamines with a chiral nitrogen centre. Free energy barriers (DG6¼) of the nitrogen inversion were estimated to be ca. 22 kcal molS1 at temperatures near 420 K using variable temperature NMR measurements in DMSO-d6. Further density functional studies of a number model systems were undertaken in order to better rationalize the measured inversion barriers and follow the role of various structural factors in raising the barrier height of the nitrogen inversion process.

Item Type: Article
Research Area: Chemistry
Faculty, School or Research Centre: Faculty of Science (until 2011)
Faculty of Science (until 2011) > School of Pharmacy and Chemistry
Depositing User: Alex Sinclair
Date Deposited: 07 Feb 2012 10:57
Last Modified: 17 Dec 2012 11:50
URI: http://eprints.kingston.ac.uk/id/eprint/17356

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