Structural Elucidation of an Atropisomeric Entcassiflavan-(4β→8)-Epicatechin Isolated from Dalbergia monetaria L.f. Based on NMR and ECD Calculations in Comparison to Experimental Data
Abstract
:1. Introduction
2. Results and Discussion
2.1. Compound Identification
2.2. Determination of the Absolute Configuration and the Biaryl Position by Means of ECD Calculation
3. Materials and Methods
3.1. General Experimental Procedures
3.2. Extraction and Isolation of Compound
3.3. Computational Methods
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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Pos. a | δ 13C (ppm) | δ 1H (ppm) m (J [Hz]) | Key HMBC (H→C) | Key NOE |
---|---|---|---|---|
C2 | 80.43 | 4.974 dd (11.6/2.0) ax | C4, B1′, B2′/6′ | C3 eq, C4, B2′/6′ |
C3 | 36.71 | 2.640 ddd (13.2/12.0/11.6) ax; 1.836 ddd (13.2/5.8/2.0) eq | C2, C4, B1′, A10, D8; B4, A10 | B2′/6′; C2, C4 |
C4 | 33.05 | 4.771 ddd (12.0/5.8/1.1) ax | B2, B3, A5, A9, A10, D7, D8, D9 | C2, C3 eq, A5 |
A5 | 129.84 | 6.709 dd (8.4/1.2) | A7, A8, A9 | A6 |
A6 | 108.99 | 6.262 dd (8.4/2.5) | A7, A8, A9, A10 | A5 |
A7 | 156.75 | - | ||
A8 | 103.97 | 6.311 d (2.5) | A6, A7, A9, A10 | |
A9 | 157.26 | - | ||
A10 | 120.12 | - | ||
B1′ | 134.77 | - | ||
B2′/6′ | 128.62 | 7.056 d-like (8.6) | B6′/2′, B4′ | B3′/5′ |
B3′/5′ | 115.95 | 6.660 d-like (8.6) | B1′, B5′/3′, B4′ | B2′/6′ |
B4′ | 157.99 | - | ||
F2 | 79.30 | 4.731 br s-like ax | F3, F4,E1′, E2′, E6′ | F3, F4ax, E2′, E6′ |
F3 | 67.44 | 4.067 ddd (4.6/2.3/1.2) eq | F2, D10 | F2, F4ax, F4eq, E2′, E6′ (w) b |
F4 | 29.35 | 2.846 dd (16.8/4.6) ax; 2.757 ddd (16.8/2.3/0.9) eq | F2, F3, D5, D9, D10; F2, F3, D5, D9, D10 | F2 ax, F3; F3 |
D5 | 156.03 | - | ||
D6 | 96.09 | 6.081 s | D5, D7, D8, D10 | |
D7 | 155.74 | - | ||
D8 | 110.05 | - | ||
D9 | 155.50 | - | ||
D10 | 100.78 | - | ||
E1′ | 131.89 | - | ||
E2′ | 114.14 | 6.540 dd (2.1/0.6) | E3′, E4′, E6′ | |
E3′ | 145.72 | - | ||
E4′ | 145.43 | - | ||
E5′ | 115.95 | 6.638 d (8.2) | E1′, E3′, E4′ | E6′ |
E6′ | 119.76 | 6.132 ddd (8.2/2.1/0.6) | E4′ | E5′ |
Biaryl Bond | Energy 1 (kcal/mol) | Config. 2- Atropoisomer | S 3 | Shift | Figure | Config. 2- Atropisomer | S 3 | Shift | Figure |
---|---|---|---|---|---|---|---|---|---|
4–8 | 0.0 | RRRR-P | 0.9674 | +19 | Figure 1A | SSSS-M | 0.6071 | −30 | Figure S8 |
4–8 | 1.7 | RRRR-M | 0.9642 | +30 | Figure 1C | SSSS-P | 0.8631 | −3 | Figure S15 |
4–8 | 0.0 | SSRR-P | 0.7511 | −26 | Figure S9 | RRSS-M | 0.6300 | +16 | Figure S10 |
4–8 | 2.4 | SSRR-M | 0.7720 | +20 | Figure S16 | RRSS-P | 0.7557 | −21 | Figure S17 |
4–6 | 0.0 | RRRR-M | 0.6709 | −5 | Figure S11 | SSSS-P | 0.7564 | −26 | Figure S18 |
4–6 | 2.3 | RRRR-P | 0.9278 | +27 | Figure 2 | SSSS-M | 0.8379 | −1 | Figure S12 |
4–6 | 0.0 | SSRR-P | 0.7730 | −30 | Figure S13 | RRSS-M | 0.8427 | +29 | Figure S20 |
4–6 | 1.3 | SSRR-M | 0.8580 | −2 | Figure S19 | RRSS-P | 0.7863 | −27 | Figure S14 |
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de Moura, P.H.B.; Brandt, W.; Porzel, A.; Martins, R.C.C.; Leal, I.C.R.; Wessjohann, L.A. Structural Elucidation of an Atropisomeric Entcassiflavan-(4β→8)-Epicatechin Isolated from Dalbergia monetaria L.f. Based on NMR and ECD Calculations in Comparison to Experimental Data. Molecules 2022, 27, 2512. https://doi.org/10.3390/molecules27082512
de Moura PHB, Brandt W, Porzel A, Martins RCC, Leal ICR, Wessjohann LA. Structural Elucidation of an Atropisomeric Entcassiflavan-(4β→8)-Epicatechin Isolated from Dalbergia monetaria L.f. Based on NMR and ECD Calculations in Comparison to Experimental Data. Molecules. 2022; 27(8):2512. https://doi.org/10.3390/molecules27082512
Chicago/Turabian Stylede Moura, Patrícia Homobono Brito, Wolfgang Brandt, Andrea Porzel, Roberto Carlos Campos Martins, Ivana Correa Ramos Leal, and Ludger A. Wessjohann. 2022. "Structural Elucidation of an Atropisomeric Entcassiflavan-(4β→8)-Epicatechin Isolated from Dalbergia monetaria L.f. Based on NMR and ECD Calculations in Comparison to Experimental Data" Molecules 27, no. 8: 2512. https://doi.org/10.3390/molecules27082512