New Compounds from the Roots of Corsican Calicotome Villosa (Poir.) Link.: Two Pterocarpans and a Dihydrobenzofuran
Abstract
:1. Introduction
2. Results and Discussion
- Compound 1, the major component of fraction F2, was isolated in pure form by repetitive CC and its structure elucidated using a combination of spectroscopic techniques including 2D NMR “INADEQUATE” (Incredible Natural Abundance DoublE QUAntum Transfer Experiment) sequence.
- As observed on their 13C NMR spectra, the sub-fractions F3.B.3 and F3.B.7 (see experimental) contained only the unidentified compounds 2 and 3 with the relative ratios 3:1 and 1:4, respectively, according to the relative intensities of signals. Although we did not succeed in isolating 2 and 3 in a pure form, the full set of 1D and 2D NMR experiments was conducted on the sub-fractions and compounds 2 and 3 were unambiguously identified.
2.1. Determination of 2-(1-methylethenyl)-5-hydroxy-6-carbomethoxy-2,3-dihydrobenzofuran (1)
2.2. Determination of 4,9-dihydroxy-3-methoxy-2-dimethylallylpterocarpan (2)
2.3. Determination of 4,9-dihydroxy-3′,3′-dimethyl-2,3-pyranopterocarpan (3)
3. Materials and Methods
3.1. Plant Material
3.2. Extraction and Isolation
3.3. NMR Spectroscopy
3.4. Mass Spectrometry
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Sample Availability: Samples of the compounds are not available from the authors. |
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N°C | δ13C (ppm) | DEPT | δ1H (ppm) | Multiplicity (J (Hz)) | HMBC (H→C) | COSY | NOESY |
2 | 85.52 | CH | 5.13 | t (8.0) | 11 | 3a; 3b | 3a; 3b; 12 |
3 | 35.27 | CH2 | 3.02 (a) 3.33 (b) | ddd (16.7; 8.0; 1.2) ddd (16.7; 8.0; 1.2) | 2; 4; 5; 8; 9; 10 | 2; 3b; 4 2; 3a; 4 | 2; 4; 12 2; 4; 12 |
4 | 113.79 | CH | 6.80 | br s | 3; 5; 6; 7; 8; 9; 13 | 3a; 3b | 3a; 3b; 5-OH |
5 | 156.86 | C | - | - | - | - | - |
6 | 110.48 | C | - | - | - | - | - |
7 | 107.40 | CH | 7.16 | s | 4; 5; 6; 8; 9; 13 | - | - |
8 | 152.34 | C | - | - | - | - | - |
9 | 136.55 | C | - | - | - | - | - |
10 | 143.67 | C | - | - | - | - | - |
11 | 112.23 | CH2 | 4.91(a) 5.07(b) | m m | 2; 10; 12 2; 3; 10; 12 | 12 | 11b; 12 11a; 12 |
12 | 17.17 | CH3 | 1.75 | br s | 2; 10; 11 | 11a; 11b | 2; 3a; 3b; 11a; 11b |
13 | 170.63 | C | - | - | - | - | - |
14 | 52.21 | CH3 | 3.91 | s | 13 | - | - |
5-OH | - | - | 10.55 | s | 4; 5; 6; 9 | - | 4 |
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N°C | δ13C (ppm) | DEPT | δ1H (ppm) | Multiplicity (J (Hz)) | HMBC (H→C) | COSY | NOESY |
1 | 121.00 | CH | 6.89 | br s | 1′; 3; 4; 4a; 11a | - | 1′; 11a |
2 | 128.72 | C | - | - | - | - | |
3 | 145.52 | C | - | - | - | - | |
4 | 137.72 | C | - | - | - | - | |
4a | 142.01 | C | - | - | - | - | |
6 | 67.04 | CH2 | 4.32 (x) 3.62 (y) | dd (10.9;4.8) t (10.9) | 4a; 6a; 6b; 11a | 6y; 6a 6x; | 6y 6x |
6a | 39.70 | CH | 3.57 | m | 6; 6b; 7; 10a | 11a; 6x | 7; 11a |
6b | 118.99 | C | - | - | - | - | |
7 | 125.01 | CH | 7.08 | d (8.6) | 6a; 9; 10; 10a | 8 | 6a; 8 |
8 | 107.75 | CH | 6.37 | m | 10; 10a | 7 | 7 |
9 | 157.02 | C | - | - | - | - | |
10 | 98.48 | CH | 6.39 | s | 6b;8;9 | - | 9-OH |
10a | 160.70 | C | - | - | - | - | |
11a | 78.44 | CH | 5.50 | d (6.6) | 1; 4a; 6; 6a; 11b | 6a | 1; 6a |
11b | 115.52 | C | - | - | - | - | |
1′ | 28.15 | CH2 | 3.33 | m | 1; 2; 2′; 3; 3′ | 2′; 4′; 5′ | 1; 2′; -OCH3 |
2′ | 122.81 | CH | 5.29 | m | 4′; 5′ | 1′; 4′; 5′ | 1′ |
3′ | 132.46 | C | - | - | - | - | |
4′ | 17.85 | CH3 | 1.74 | br s | 2′; 3′; 5′ | 1′; 2′ | |
5′ | 25.83 | CH3 | 1.74 | br s | 2′; 3′; 4′ | 1′; 2′ | |
-OCH3 | 60.62 | - | 3.86 | s | 3 | - | 1′ |
4-OH | - | - | 5.47 | s | 3; 4; 4a | - | - |
9-OH | - | - | 4.95 | s | 8; 9; 10 | - | 10 |
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N°C | δ13C (ppm) | DEPT | δ1H (ppm) | Multiplicity (J (Hz)) | HMBC (H→C) | COSY | NOESY |
1 | 118.41 | CH | 6.77 | s | 1′; 2; 3; 4; 4a; 11a | - | 1′; 11a |
2 | 116.12 | C | - | - | - | - | |
3 | 140.30 | C | - | - | - | - | |
4 | 133.01 | C | - | - | - | - | |
4a | 143.73 | C | - | - | - | - | |
6 | 66.92 | CH2 | 4.34 (x) 3.63 (y) | dd (10.8; 5.0) t (10.8) | 4a; 6a; 6b; 11a | 6y; 6a 6x | 6y; 6a 6x; |
6a | 39.53 | CH | 3.53 | m | 6; 6b; 7; 10a; 11a | 11a; 6x | 6x; 11a |
6b | 119.00 | C | - | - | - | - | - |
7 | 125.04 | CH | 7.08 | d (8.3) | 6; 6a; 6b; 9; 10; 10a | 8 | 8 |
8 | 107.77 | CH | 6.37 | m | 6b | 7 | 7 |
9 | 157.07 | C | - | - | - | - | |
10 | 98.44 | CH | 6.38 | s | 6b; 8; 9; 10a | - | |
10a | 160.63 | C | - | - | - | - | |
11a | 78.57 | CH | 5.48 | d (6.5) | 1; 2; 4a; 6; 6a; 11b | 6a | 1; 6a |
11b | 112.65 | C | - | - | - | - | |
1′ | 121.79 | CH | 6.31 | d (9.8) | 1; 2; 3; 3′; 4; 5′ | 2′ | 1; 2′ |
2′ | 129.39 | CH | 5.57 | d (9.8) | 2; 3; 3′; 4′ | 1′ | 1′; 4′; 5′ |
3′ | 77.31 | C | - | - | - | - | - |
4′ * | 28.16 | CH3 | 1.48 | s | 1′; 2′; 3; 3′; 5′ | 2′ | |
5′ * | 27.90 | CH3 | 1.44 | s | 1′; 2′; 3′; 4′ | 2′ | |
4-OH | - | - | 5.38 #,$ | s | - | - | - |
9-OH | - | - | 5.28 #,$ | m | - | - | - |
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Palu, D.S.; Paoli, M.; Casabianca, H.; Casanova, J.; Bighelli, A. New Compounds from the Roots of Corsican Calicotome Villosa (Poir.) Link.: Two Pterocarpans and a Dihydrobenzofuran. Molecules 2020, 25, 3467. https://doi.org/10.3390/molecules25153467
Palu DS, Paoli M, Casabianca H, Casanova J, Bighelli A. New Compounds from the Roots of Corsican Calicotome Villosa (Poir.) Link.: Two Pterocarpans and a Dihydrobenzofuran. Molecules. 2020; 25(15):3467. https://doi.org/10.3390/molecules25153467
Chicago/Turabian StylePalu, Doreen Stacy, Mathieu Paoli, Hervé Casabianca, Joseph Casanova, and Ange Bighelli. 2020. "New Compounds from the Roots of Corsican Calicotome Villosa (Poir.) Link.: Two Pterocarpans and a Dihydrobenzofuran" Molecules 25, no. 15: 3467. https://doi.org/10.3390/molecules25153467