[en] The peculiar isomer-selective reduction of (α)-hydroxyiminophosphonates (oxime isomers) into (α)-hydroxyaminophosphonate (hydroxylamine) derivatives is presented. A library of 16 (α)-hydroxyiminophosphonates is prepared and studied via a unique multifaceted approach involving the interplay of NMR, XRD, MS, IM-MS and computational chemistry techniques. The combination of NMR, XRD and HPLC enables the seamless separation, identification and quantification of the oxime isomers (E/Z). Tandem MS (MS/MS) enables the determination of the fragmentation patterns for both isomers. Collision energy breakdown curves highlight the order of apparition of the fragments as well as their related energy of fragmentation, demonstrating that the strength of the C-P bond in the Z isomers is much weaker than in the E isomers. Computational chemistry demonstrates that favorable protonation site is isomer-dependent with the phosphonate moiety being the favorable protonation site for the E isomers, while protonation occurs preferentially on the amino moiety for Z isomers regardless of the phosphite source. The combination of these various methods led an unprecedented level of characterization of oxime isomers, providing a better uderstanding of the isomer-dependent behavior of (α)-hydroxyiminophosphonates. This journal is
Disciplines :
Chemistry
Author, co-author :
Toupy, Thomas ; Université de Liège - ULiège > Université de Liège - ULiège
Kune, Christopher ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de spectrométrie de masse (L.S.M.)
Van Hecke, Kristof ; XStruct, Department of Chemistry, Ghent University, Ghent, Belgium
Quinton, Loïc ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie biologique
ULiège - Université de Liège [BE] FRIA - Fonds pour la Formation à la Recherche dans l'Industrie et dans l'Agriculture [BE] F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE] FWO - Fonds Wetenschappelijk Onderzoek Vlaanderen [BE]
Funding text :
This work was supported by the University of Liège (Welcome Grant WG-13/03, J. C. M. M.) and the F.R.S.-FNRS (Incentive grant for scientific research MIS F453020F, J. C. M. M.). Computational have been provided by the “Consortium des Équipements de Calcul Intensif” (CÉCI), funded by the “Fonds de la Recherche Scientifique de Belgique” (F.R.S.-FNRS) under Grant No. 2.5020.11. T. T. is a FRIA PhD fellow. K. V. H. thanks the Research Foundation – Flanders (FWO) (projects AUGE/11/029 and G099319N) for funding.
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