Revisiting the Absolute Configuration of Peyssonnoside A Using Vibrational Circular Dichroism Spectroscopy
Peyssonnoside A is an unusual natural product consisting of a diterpene unit and a sulfonated monosaccharide. The experimental and theoretical comparison of Optical Rotatory Dispersion (ORD) and quantitative Nuclear Magnetic Resonance (NMR) data provided strong evidence for the stereochemistry of th...
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MDPI AG
2024-01-01
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| Series: | Symmetry |
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| Online Access: | https://www.mdpi.com/2073-8994/16/2/133 |
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| author | Andrew R. Puente Bhuwan Khatri Chhetri Julia Kubanek Prasad L. Polavarapu |
| author_facet | Andrew R. Puente Bhuwan Khatri Chhetri Julia Kubanek Prasad L. Polavarapu |
| author_sort | Andrew R. Puente |
| collection | DOAJ |
| description | Peyssonnoside A is an unusual natural product consisting of a diterpene unit and a sulfonated monosaccharide. The experimental and theoretical comparison of Optical Rotatory Dispersion (ORD) and quantitative Nuclear Magnetic Resonance (NMR) data provided strong evidence for the stereochemistry of the diterpene unit. However, predicted Vibrational Circular Dichroism (VCD) spectra of Peyssonnoside A at the B3LYP/6-311++G(2d,2p) level showed poor correlation to the corresponding experimental spectra, preventing independent absolute configuration (AC) determination from VCD analysis. New calculations using the B3PW91 functional and the 6-311G(3df,2pd) basis set suggest that we can now independently and confidently assign the AC of Peyssonnoside A through VCD analyses. The use of f-polarization functions is responsible for the current successful assignment, compared to previously failed VCD analysis. This study highlights two important points: (a) the importance of using multiple levels of theories for satisfactorily reproducing the experimental spectra and (b) for quantitative comparisons using similarity indices, it is important to consider not only the VCD spectra but also the corresponding absorption spectra. |
| first_indexed | 2024-03-07T22:12:09Z |
| format | Article |
| id | doaj.art-8420c9ad204f49e79c0f7a5668e758ab |
| institution | Directory Open Access Journal |
| issn | 2073-8994 |
| language | English |
| last_indexed | 2024-03-07T22:12:09Z |
| publishDate | 2024-01-01 |
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| record_format | Article |
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| spelling | doaj.art-8420c9ad204f49e79c0f7a5668e758ab2024-02-23T15:35:47ZengMDPI AGSymmetry2073-89942024-01-0116213310.3390/sym16020133Revisiting the Absolute Configuration of Peyssonnoside A Using Vibrational Circular Dichroism SpectroscopyAndrew R. Puente0Bhuwan Khatri Chhetri1Julia Kubanek2Prasad L. Polavarapu3Department of Chemistry, Vanderbilt University, Nashville, TN 37235, USASchool of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332, USASchool of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332, USADepartment of Chemistry, Vanderbilt University, Nashville, TN 37235, USAPeyssonnoside A is an unusual natural product consisting of a diterpene unit and a sulfonated monosaccharide. The experimental and theoretical comparison of Optical Rotatory Dispersion (ORD) and quantitative Nuclear Magnetic Resonance (NMR) data provided strong evidence for the stereochemistry of the diterpene unit. However, predicted Vibrational Circular Dichroism (VCD) spectra of Peyssonnoside A at the B3LYP/6-311++G(2d,2p) level showed poor correlation to the corresponding experimental spectra, preventing independent absolute configuration (AC) determination from VCD analysis. New calculations using the B3PW91 functional and the 6-311G(3df,2pd) basis set suggest that we can now independently and confidently assign the AC of Peyssonnoside A through VCD analyses. The use of f-polarization functions is responsible for the current successful assignment, compared to previously failed VCD analysis. This study highlights two important points: (a) the importance of using multiple levels of theories for satisfactorily reproducing the experimental spectra and (b) for quantitative comparisons using similarity indices, it is important to consider not only the VCD spectra but also the corresponding absorption spectra.https://www.mdpi.com/2073-8994/16/2/133Peyssonnoside Anatural productsvibrational circular dichroismoptical rotationdensity functional calculations |
| spellingShingle | Andrew R. Puente Bhuwan Khatri Chhetri Julia Kubanek Prasad L. Polavarapu Revisiting the Absolute Configuration of Peyssonnoside A Using Vibrational Circular Dichroism Spectroscopy Symmetry Peyssonnoside A natural products vibrational circular dichroism optical rotation density functional calculations |
| title | Revisiting the Absolute Configuration of Peyssonnoside A Using Vibrational Circular Dichroism Spectroscopy |
| title_full | Revisiting the Absolute Configuration of Peyssonnoside A Using Vibrational Circular Dichroism Spectroscopy |
| title_fullStr | Revisiting the Absolute Configuration of Peyssonnoside A Using Vibrational Circular Dichroism Spectroscopy |
| title_full_unstemmed | Revisiting the Absolute Configuration of Peyssonnoside A Using Vibrational Circular Dichroism Spectroscopy |
| title_short | Revisiting the Absolute Configuration of Peyssonnoside A Using Vibrational Circular Dichroism Spectroscopy |
| title_sort | revisiting the absolute configuration of peyssonnoside a using vibrational circular dichroism spectroscopy |
| topic | Peyssonnoside A natural products vibrational circular dichroism optical rotation density functional calculations |
| url | https://www.mdpi.com/2073-8994/16/2/133 |
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