Stereochemical Study of the Super Large Tetrakis Alkaloid Alasmontamine A by Means of an Advanced Computational NMR
Abstract
:1. Introduction
2. Results and Discussion
3. Materials and Methods
3.1. Conformational Search and Geometry Optimization
3.2. Calculation of Chemical Shifts
3.3. Topological Analysis
3.4. Estimation of Probability Distribution of Diastereomers
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Abbreviations
BCP | Bond Critical Point |
CMAE | Corrected Mean Absolute Error |
COSY | COrrelated SpectroscopY |
DFT | Density Functional Theory |
HMBC | Heteronuclear Multiple Bond Correlation |
HOHAHA | HOmonuclear HArtmann–HAhn spectroscopy |
HSQC | Heteronuclear Single Quantum Coherence |
IEF-PCM | Equation Formalism Polarizable Continuum Model |
IUPAC | International Union of Pure and Applied Chemistry |
MAE | Mean Absolute Error |
NCMAE | Normalized Corrected Mean Absolute Error |
NMR | Nuclear Magnetic Resonance |
NOESY | Nuclear Overhauser Effect SpectroscopY |
NRMSD | Normalized Root-Mean-Square Deviation |
PES | Potential Energy Surface |
PBE | Perdew–Burke–Ernzerhof (functional) |
QTAIM | Atoms in Molecules |
RMSD | Root-Mean-Square Deviation: A Quantum Theory |
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Nucleus | 0 | 15′ | 15‴ | Exp. |
---|---|---|---|---|
1H NMR | ||||
H-3α | 3.97 (0.29) | 4.00 (0.26) | 3.98 (0.28) | 4.26 |
H-9 | 7.15 (0.41) | 7.24 (0.32) | 7.15 (0.41) | 7.56 |
H-18α | 4.06 (−0.23) | 4.12 (−0.29) | 4.09 (−0.26) | 3.83 |
H-21 | 4.18 (0.31) | 4.17 (0.32) | 4.15 (0.34) | 4.49 |
H-17″β | 2.36 (0.30) | 2.41 (0.25) | 2.35 (0.31) | 2.66 |
H-23″α | 4.36 (0.37) | 4.29 (0.44) | 4.36 (0.37) | 4.73 |
13C NMR | ||||
C-11′ | 114.2 (2.3) | 114.0 (2.5) | 114.1 (2.4) | 116.5 |
C-21′ | 62.6 (2.1) | 69.7 (−5.0) | 62.6 (2.1) | 64.7 |
C-22′ | 31.5 (−2.2) | 32.1 (−2.8) | 31.8 (−2.5) | 29.3 |
C-15″ | 84.6 (2.5) | 84.3 (2.8) | 84.5 (2.6) | 87.1 |
C-22″ | 166.5 (2.1) | 166.5 (2.1) | 166.5 (2.1) | 168.6 |
C-7‴ | 58.1 (−2.1) | 58.4 (−2.4) | 57.8 (−1.8) | 56.0 |
C-8‴ | 137.8 (−1.9) | 138.1 (−2.2) | 135.8 (0.1) | 135.9 |
C-9‴ | 120.0 (−4.1) | 119.7 (−3.8) | 120.2 (−4.3) | 115.9 |
C-11‴ | 124.1 (−5.2) | 121.7 (−2.8) | 124.2 (−5.3) | 118.9 |
C-12‴ | 138.7 (3.3) | 138.1 (3.9) | 138.3 (3.7) | 142.0 |
C-13‴ | 141.2 (−4.3) | 140.7 (−3.8) | 141.2 (−4.3) | 136.9 |
C-21‴ | 62.3 (2.4) | 62.3 (2.4) | 69.5 (−4.8) | 64.7 |
C-23‴ | 43.1 (2.1) | 43.0 (2.2) | 43.2 (2.0) | 45.2 |
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Semenov, V.A.; Krivdin, L.B. Stereochemical Study of the Super Large Tetrakis Alkaloid Alasmontamine A by Means of an Advanced Computational NMR. Int. J. Mol. Sci. 2023, 24, 5572. https://doi.org/10.3390/ijms24065572
Semenov VA, Krivdin LB. Stereochemical Study of the Super Large Tetrakis Alkaloid Alasmontamine A by Means of an Advanced Computational NMR. International Journal of Molecular Sciences. 2023; 24(6):5572. https://doi.org/10.3390/ijms24065572
Chicago/Turabian StyleSemenov, Valentin A., and Leonid B. Krivdin. 2023. "Stereochemical Study of the Super Large Tetrakis Alkaloid Alasmontamine A by Means of an Advanced Computational NMR" International Journal of Molecular Sciences 24, no. 6: 5572. https://doi.org/10.3390/ijms24065572