Sampling CASE Application for the Quality Control of Published Natural Product Structures
Abstract
:1. Introduction
2. Results
2.1. Luteolin 8-C-E-Propenoic Acid
2.2. Tomentodiplacone
2.3. Kadangustin A
2.4. Berkeleyamide D
2.5. 14-Norpseurotin A
2.6. Feruloylpodospermic Acid A
2.7. Cochinchistemoninone
2.8. Milicifoline B
2.9. 5-Cyprinol Sulfate
2.10. Viridiol aka TAEMC161
3. Discussion & Conclusions
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
Abbreviations
ADEQ | 1,1–ADEQUATE (“” equivalent) |
CASE | Computer Aided Structure Elucidation |
COSY | H,H-Correlated Spectroscopy () |
distance | |
C | NMR carbon chemical shift |
H | NMR proton chemical shift |
average deviation of the calculated chemical shift to the experimentally observed value | |
exp. | experimental |
H2BC | HMQC-COSY |
NMR | Nuclear Magnetic Resonance |
NOE | Nuclear Overhauser Effect |
X-HMBC | H,X-Heteronuclear Multiple Bond Correlation ( and ) |
Appendix A. All Assigned Back-Calculated Chemical Shifts
References
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Molecule | # Inspected | Confirmed |
---|---|---|
Luteolin 8-C-E-propenoic acid | 6 | yes |
Tomentodiplacone | 2 | yes |
Kadangustin A | 5 | no |
Berkeleyamide D | 2 | no |
14-norpseurotin A | 2 | no |
Feruloylpodospermic acid A | 2 | no |
Cochinchistemoninone | 3 | no |
Milicifoline B | 3 | pending further analysis |
5-cyprinol sulfate | 4 | yes |
viridiol aka TAEMC161 | >3 | yes |
C [ppm] | |||||||
---|---|---|---|---|---|---|---|
Atom | Exp. | 1-A | 1-B | 1-C | 1-D | 1-E | 1-F |
1 | 169.0 | 171.5 | 171.5 | 171.5 | - | 170.4 | - |
2 | 182.2 | 182.1 | 160.5 | 160.5 | 187.0 | 175.0 | 189.7 |
1.3 | 12.1 | 12.1 | 2.4 | 4.3 | 3.8 | ||
Etotal [kcal/mol] | 26 | 29 | 45 | 80 | 74 | 303 |
C [ppm] | |||
---|---|---|---|
Atom | Exp. | 2-A | 2-B |
1 | 164.4 | 162.5 | 182.6 |
2 | 196.4 | 196.8 | 170.0 |
1.2 | 22.3 | ||
Etotal [kcal/mol] | 62 | 64 |
C [ppm] | ||||||
---|---|---|---|---|---|---|
Atom | Exp. | 3-A | 3-B | 3-C | 3-D | 3-E |
1 | 172.0 | 170.2 | 162.1 | 165.0 | 165.4 | 171.4 |
2 | 39.3 | 31.3 | 33.6 | 33.6 | 35.9 | 46.7 |
3 | 34.8 | 34.8 | 38.7 | 38.7 | 31.1 | 41.8 |
3.3 | 6.5 | 5.5 | 4.6 | 5.0 | ||
4.2 | 7.1 | 6.0 | 1.8 | 4.5 | ||
8.0 | 13.8 | 10.9 | 6.6 | 8.0 | ||
Etotal [kcal/mol] | 160 | 165 | 160 | 168 | 156 |
C [ppm] | H [ppm] | |||||
---|---|---|---|---|---|---|
Atom | Exp. | 4-A | 4-B | Exp. | 4-A | 4-B |
4 | 84.9 | 76.6 | 87.2 | |||
6 | 95.3 | 100.1 | 90.2 | |||
7 | 4.41 | 4.42 | 4.0 | |||
8 | 197.7 | 165.5 * | 198.0 | |||
9 | 104.4 | 105.6 | 98.8 | 5.35 | 4.85 | 5.1 |
10 | 199.4 | 204.9 | 196.5 | |||
11 | 37.4 | 45.0 | 55.7 * | 3.98 | 3.22 | 4.2 |
8.5 | 4.9 | 0.5 | 0.3 | |||
Etotal [kcal/mol] | 67 | 24 |
4-A | 4-B | ||||
---|---|---|---|---|---|
Atom | Exp. | M-I | M-II | M-I | M-II |
1 | 23.9 | 23.5 | 23.8 | 23.5 | 23.8 |
2 | 24.0 | 23.6 | 24.0 | 23.9 | 24.0 |
3 | 45.5 | 47.1 | 45.5 | 44.3 | 45.4 |
4 | 84.9 | 76.6 | 84.9 | 87.2 | 85.5 |
5 | 164.1 | 169.2 | 171.6 | 169.2 | 170.2 |
6 | 95.3 | 100.1 | 95.3 | 90.2 | 65.4 |
7 | 75.1 | 76.5 | 75.1 | 78.5 | 75.7 |
8 | 197.8 | 204.9 | 181.2 | 198.0 | 156.9 |
9 | 104.4 | 105.6 | 104.4 | 98.8 | 89.6 |
10 | 199.4 | 165.5 | 199.4 | 196.5 | 198.4 |
11 | 37.4 | 45.0 | 43.0 | 55.7 | 47.5 |
12 | 133.2 | 137.4 | 133.2 | 135.6 | 134.6 |
13 | 129.2 | 129.0 | 129.2 | 129.6 | 129.6 |
14 | 129.2 | 128.6 | 129.2 | 129.2 | 128.9 |
15 | 127.0 | 125.7 | 127.1 | 127.6 | 127.1 |
16 | 129.2 | 128.6 | 129.2 | 129.2 | 128.9 |
17 | 129.2 | 129.0 | 129.2 | 129.6 | 129.6 |
18 | 23.8 | 23.5 | 23.8 | 23.5 | 23.8 |
9.0 | 4.6 | 5.1 | 12.5 | ||
41.5 | 24.1 | 23.9 | 51.0 |
C [ppm] | H [ppm] | |||||
---|---|---|---|---|---|---|
Atom | Exp. | 5-A | 5-B | Exp. | 5-A | 5-B |
1 | 185.7 | 167.3 | 188.0 | |||
2 | 70.4 | 69.7 | 69.8 | 4.78 | 4.0 | 4.2 |
3 | 70.3 | 71.6 | 88.9 | 4.62 | 4.0 | 4.2 |
4 | 73.2 | 68.1 | 70.1 | 4.70 | 5.0 | 4.8 |
6.4 | 6.2 | 0.6 | 0.4 | |||
Etotal [kcal/mol] | 160 | 148 |
C [ppm] | |||
---|---|---|---|
Atom | Exp. | 6-A | 6-B |
1 | 170.4 | 171.0 | 173.2 |
2 | 38.9 | 39.2 | 35.9 |
3 | 83.5 | 78.9 | 85.3 |
4 | 34.1 | 38.4 | 34.0 |
5 | 173.1 | 170.2 | 173.1 |
2.5 | 1.5 | ||
Etotal [kcal/mol] | 75 | 56 |
C [ppm] | ||||
---|---|---|---|---|
Atom | Exp. | 7-A | 7-B | 7-C |
1 | 208.9 | 211.2 | 211.3 | 211.3 |
2 | 90.6 | 117.6 | 127.4 | 103.3 |
3 | 169.2 | 171.8 | 182.6 | 191.4 |
4 | 98.4 | 98.7 | 88.1 | 95.6 |
5 | 173.1 | 175.2 | 197.9 | 167.3 |
6.9 | 17.5 | 9.2 | ||
Etotal [kcal/mol] | 116 | 87 | 80 |
C [ppm] | ||||
---|---|---|---|---|
Atom | Exp. | 8-A | 8-B | 8-C |
1 | 144.1 | 145.5 | 145.5 | 139.6 |
2 | 142.8 | 136.9 | 144.4 | 91.7 |
3.6 | 1.5 | 27.8 | ||
Etotal [kcal/mol] | 267 | 288 | 265 |
[pm] | ||
---|---|---|
NOE | 8-A | 8-B |
1 | 705 | 850 |
2 | 612 | 618 |
2 | 503 | 832 |
C [ppm] | |||||
---|---|---|---|---|---|
Atom | Exp. | 9-A | 9-B | 9-C | 9-D |
1 | 67.6 | 77.7 | 64.2 | 64.2 | 64.2 |
2 | 72.3 | 73.3 | 73.3 | 73.3 | 87.6 |
3 | 68.4 | 68.4 | 91.5 | 68.4 | 68.4 |
4 | 71.4 | 71.4 | 71.4 | 89.5 | 71.4 |
2.8 | 6.9 | 5.6 | 4.7 | ||
Etotal [kcal/mol] | 42 | 48 | 56 | 53 |
Atom | Exp. | M-I | M-II | M-IIIa | M-IIIb |
---|---|---|---|---|---|
1 | 60.7 | 60.8 | 57.8 | 61.0 | 60.4 |
2 | 81.7 | 82.0 | 88.9 | 93.6 | 89.5 |
3 | 61.6 | 70.4 | 66.1 | 68.8 | 69.3 |
4 | 122.1 | 138.8 | 164.0 | 154.2 | 158.8 |
5 | 145.6 | 116.1 | 110.4 | 126.6 | 111.6 |
6 | 173.4 | 161.1 | 162.6 | 174.0 | 165.8 |
7 | 142.4 | 118.6 | 116.5 | 133.2 | 130.4 |
8 | 42.3 | 47.3 | 44.8 | 55.5 | 55.1 |
9 | 71.7 | 71.9 | 80.7 | 80.0 | 75.9 |
10 | 30.5 | 28.0 | 21.0 | 22.7 | 22.1 |
11 | 158.6 | 157.2 | 145.4 | 172.3 | 169.7 |
12 | 127.3 | 125.4 | 125.1 | 131.4 | 128.8 |
13 | 127.3 | 126.6 | 123.7 | 131.6 | 130.9 |
14 | 129.8 | 133.9 | 133.9 | 142.8 | 144.9 |
15 | 158.0 | 150.7 | 137.8 | 154.4 | 158.5 |
16 | 136.9 | 131.5 | 124.5 | 136.9 | 137.6 |
17 | 145.7 | 146.4 | 148.6 | 167.9 | 172.1 |
18 | 28.4 | 29.0 | 24.3 | 28.8 | 28.6 |
19 | 36.5 | 35.7 | 36.6 | 38.3 | 39.3 |
20 | 206.7 | 206.8 | 206.2 | 213.0 | 210.5 |
RMSD | 10.2 | 15.6 | 12.1 | 14.4 |
Atom | Exp. | M-I | M-II | M-IIIa | M-IIIb |
---|---|---|---|---|---|
1 | 60.7 | 60.8 | 57.8 | 61.6 | 59.8 |
2 | 81.7 | 81.7 | 88.9 | 99.4 | 96.9 |
3 | 61.6 | 69.1 | 62.9 | 79.2 | 76.1 |
4 | 122.1 | 122.1 | 127.5 | 129.0 | 123.8 |
5 | 145.6 | 138.3 | 149.3 | 158.5 | 158.4 |
6 | 173.4 | 158.0 | 153.4 | 171.1 | 163.0 |
7 | 142.4 | 142.4 | 153.0 | 165.6 | 174.0 |
8 | 42.3 | 53.7 | 48.0 | 58.6 | 59.1 |
9 | 71.7 | 71.1 | 80.7 | 83.2 | 83.3 |
10 | 30.5 | 20.5 | 21.0 | 21.1 | 20.0 |
11 | 158.6 | 158.6 | 145.4 | 171.9 | 166.3 |
12 | 127.3 | 122.0 | 125.1 | 131.4 | 129.1 |
13 | 127.3 | 127.3 | 123.7 | 131.0 | 129.0 |
14 | 129.8 | 136.9 | 133.9 | 143.3 | 145.4 |
15 | 158.0 | 139.2 | 137.8 | 157.8 | 159.8 |
16 | 136.9 | 129.6 | 134.0 | 140.2 | 141.9 |
17 | 145.7 | 123.5 | 124.5 | 138.0 | 129.5 |
18 | 28.4 | 28.4 | 24.1 | 32.9 | 31.3 |
19 | 36.5 | 36.5 | 36.6 | 39.0 | 39.5 |
20 | 206.7 | 206.7 | 206.2 | 214.2 | 211.6 |
RMSD | 8.8 | 9.8 | 11.0 | 12.0 |
Atom | Exp. | M-I | M-II | M-IIIa | M-IIIb |
---|---|---|---|---|---|
1 | 60.7 | 60.8 | 57.5 | 59.8 | 59.5 |
2 | 81.7 | 82.0 | 78.9 | 94.5 | 90.2 |
3 | 61.6 | 68.5 | 64.7 | 63.8 | 63.8 |
4 | 122.1 | 121.0 | 125.9 | 130.9 | 128.5 |
5 | 145.6 | 146.3 | 144.5 | 155.5 | 153.2 |
6 | 173.4 | 178.9 | 173.0 | 153.8 | 154.8 |
7 | 142.4 | 140.4 | 146.6 | 149.6 | 149.4 |
8 | 42.3 | 45.7 | 39.2 | 51.9 | 49.0 |
9 | 71.7 | 73.7 | 85.9 | 81.7 | 76.2 |
10 | 30.5 | 20.2 | 23.5 | 31.5 | 32.4 |
11 | 158.6 | 153.9 | 149.3 | 171.5 | 165.7 |
12 | 127.3 | 127.3 | 125.3 | 137.4 | 132.1 |
13 | 127.3 | 127.4 | 128.4 | 133.3 | 132.2 |
14 | 129.8 | 133.2 | 134.1 | 141.4 | 143.9 |
15 | 158.0 | 144.1 | 141.1 | 165.0 | 168.8 |
16 | 136.9 | 126.5 | 126.4 | 141.2 | 137.7 |
17 | 145.7 | 148.0 | 145.3 | 180.8 | 178.9 |
18 | 28.4 | 28.4 | 23.5 | 32.9 | 33.2 |
19 | 36.5 | 36.2 | 36.2 | 38.9 | 39.6 |
20 | 206.7 | 206.3 | 206.2 | 214.2 | 211.7 |
RMSD | 5.2 | 6.5 | 11.8 | 10.5 |
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Moreira, L.M.G.; Junker, J. Sampling CASE Application for the Quality Control of Published Natural Product Structures. Molecules 2021, 26, 7543. https://doi.org/10.3390/molecules26247543
Moreira LMG, Junker J. Sampling CASE Application for the Quality Control of Published Natural Product Structures. Molecules. 2021; 26(24):7543. https://doi.org/10.3390/molecules26247543
Chicago/Turabian StyleMoreira, Lorena Martins Guimarães, and Jochen Junker. 2021. "Sampling CASE Application for the Quality Control of Published Natural Product Structures" Molecules 26, no. 24: 7543. https://doi.org/10.3390/molecules26247543