Density functional and spectroscopic studies of nitrogen inversion in substituted dizocilpines.
J PHYS ORG CHEM
607 - 612.
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 (Delta G(not equal)) of the nitrogen inversion were estimated to be ca. 22 kcal mol(-1) at temperatures near 420 K using variable temperature NMR measurements in DMSO-d(6). 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. Copyright (C) 2008 John Wiley & Sons, Ltd.
|Title:||Density functional and spectroscopic studies of nitrogen inversion in substituted dizocilpines|
|Keywords:||dizocilpine, hydroxylamines, nitrogen inversion, chiral nitrogen, energy barrier, transition state, NMR spectroscopy, DFT calculations, OXAZIRIDINES, ANTAGONISTS, RECEPTORS, MK-801|
|UCL classification:||UCL > School of Life and Medical Sciences
UCL > School of Life and Medical Sciences > Faculty of Brain Sciences
UCL > School of Life and Medical Sciences > Faculty of Brain Sciences > Institute of Neurology
UCL > School of Life and Medical Sciences > Faculty of Brain Sciences > Institute of Neurology > Clinical and Experimental Epilepsy
UCL > School of BEAMS > Faculty of Maths and Physical Sciences
UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry
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