31P NMR parameters may facilitate the stereochemical analysis of phosphorus-containing compounds

Tichotová, Markéta; Ešnerová, Aneta; Tučková, Lucie; Bednářová, Lucie; Cı́sařová, Ivana; Baszczyňski, Ondřej; Procházková, Eliška

doi:10.1016/j.jmr.2022.107149

Cited by 4 publications

(14 citation statements)

References 57 publications

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“…Subsequently, we applied the docking approach to mildly ( 2 , n Conf 20 = 2) and highly flexible compounds ( 3 , n Conf 20 = 8) that have been studied in our previous work. 21 Both 2 and 3 were characterized in our previous study 21 by means of NMR spectroscopy. Therein, also the absolute configuration of 2- SR and 2- RR was determined by X-ray diffraction.…”

Section: Resultsmentioning

confidence: 99%

Exploring the impact of alignment media on RDC analysis of phosphorus-containing compounds: a molecular docking approach

Tichotová,

Tučková,

Kocek

et al. 2024

Phys. Chem. Chem. Phys.

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Section: Resultsmentioning

confidence: 99%

Exploring the impact of alignment media on RDC analysis of phosphorus-containing compounds: a molecular docking approach

Tichotová,

Tučková,

Kocek

et al. 2024

Phys. Chem. Chem. Phys.

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“…We next chose our own set of phosphorus compounds ( Figure 5 , 11 – 29 ; for simplicity compounds 30 – 34[O] discussed later are included in the MAD/RMSD values here). This was done to to determine if the calculation and scaling would be accurate enough to distinguish stereoisomers via chemical shifts rather than coupling constants [ 72 – 73 ] and provide confirmation of unusual structures and chemical shifts, and with the further stipulation that multiple P–C bonding would likely give inaccurate M06-2X NMR calculations ( Table 3 ; results with the IGLO-III basis set are included in Supporting Information File 1 , Tables S6–S9, and as expected gave higher MAD/RMSD values). The M06-2X (optimization) and B3LYP (NMR) functional combination gave the best MAD/RMSD, and the relatively low RMSD is consistent with the fact that there were no glaring discrepancies in experimental and calculated chemical shifts, both for the initial group of 1a – 10 ( Table 2 ) and the new group of 11 – 34[O] .…”

Section: Resultsmentioning

confidence: 99%

“…later are included in the MAD/RMSD values here). This was done to to determine if the calculation and scaling would be accurate enough to distinguish stereoisomers via chemical shifts rather than coupling constants[72,73] and provide confirmation of unusual structures and chemical shifts, and with the further stipulation that multiple P-C bonding would likely give inaccurate M06-2X NMR calculations (Table3; results with the IGLO-III basis set are included in…”

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Improving the accuracy of ³¹P NMR chemical shift calculations by use of scaling methods

Hersh¹,

Chan²

2023

Beilstein J. Org. Chem.

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Calculation of 31P NMR chemical shifts for a series of tri- and tetracoordinate phosphorus compounds using several basis sets and density functional theory (DFT) functionals gave a modest fit to experimental chemical shifts, but an excellent linear fit when plotted against the experimental values. The resultant scaling methods were then applied to a variety of “large” compounds previously selected by Latypov et al. and a set of stereoisomeric and unusual compounds selected here. No one method was best for all structural types. For compounds that contain P–P bonds and P–C multiple bonds, the Latypov et al. method using the PBE0 functional was best (mean absolute deviation/root mean square deviation (MAD/RMSD) = 6.9/8.5 ppm and 6.6/8.2 ppm, respectively), but for the full set of compounds gave higher deviations (MAD/RMSD = 8.2/12.3 ppm), and failed by over 60 ppm for a three-membered phosphorus heterocycle. Use of the M06-2X functional for both the structural optimization and NMR chemical shift calculation was best overall for the compounds without P–C multiple bonds (MAD/RMSD = 5.4/7.1 ppm), but failed by 30–49 ppm for compounds having any P–C multiple-bond character. Failures of these magnitudes have not been reported previously for these widely used functionals. These failures were then used to screen a variety of recommended functionals, leading to better overall methods for calculation of these chemical shifts: optimization with the M06-2X functional and NMR calculation with the PBE0 or ωB97x-D functionals gave values for MAD/RMSD = 6.9/8.5 ppm and 6.8/9.1 ppm, respectively, over an experimental chemical shift range of −181 to 356 ppm. Due to the unexplained failures observed, we recommend use of more than one method when looking at novel structures.

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“…7, kombinací s kvantově-chemickými výpočty 25,26 lze určit relativní konfiguraci na základě J C-P (cit. 27 ).…”

Section: Stereochemická Analýza Využívající 31 P Nmr Parametryunclassified

“…Obr. 8 ukazuje korelace mezi experimentálními a vypočtenými RDC, které určují relativní konfiguraci RR izomeru 27 .…”

Section: Stereochemická Analýza Využívající 31 P Nmr Parametryunclassified

Advanced NMR Spectroscopy Methods for Study of Structure and Properties of Small Molecules

Procházková

2022

Chem. Listy

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NMR spectroscopy is the key analytical method for determination of chemical structure and investigation of physico-chemical properties, such as non-covalent interactions, tautomeric equilibria or polymorphism. In this work, selected examples of using advanced NMR methods in structural analysis are discussed. (1) NMR spectroscopy with in situ irradiation useful to monitor photochemical processes, (2) 31P NMR spectroscopy for reaction monitoring and probing stereochemistry and (3) solid-state NMR spectroscopy to investigate polymorphism.

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31P NMR parameters may facilitate the stereochemical analysis of phosphorus-containing compounds

Cited by 4 publications

References 57 publications

Exploring the impact of alignment media on RDC analysis of phosphorus-containing compounds: a molecular docking approach

Exploring the impact of alignment media on RDC analysis of phosphorus-containing compounds: a molecular docking approach

Improving the accuracy of ³¹P NMR chemical shift calculations by use of scaling methods

Advanced NMR Spectroscopy Methods for Study of Structure and Properties of Small Molecules

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31P NMR parameters may facilitate the stereochemical analysis of phosphorus-containing compounds

Cited by 4 publications

References 57 publications

Exploring the impact of alignment media on RDC analysis of phosphorus-containing compounds: a molecular docking approach

Exploring the impact of alignment media on RDC analysis of phosphorus-containing compounds: a molecular docking approach

Improving the accuracy of 31P NMR chemical shift calculations by use of scaling methods

Advanced NMR Spectroscopy Methods for Study of Structure and Properties of Small Molecules

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Product

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Improving the accuracy of ³¹P NMR chemical shift calculations by use of scaling methods