New Benzofuran Oligomers from the Roots of Eupatorium heterophyllum Collected in China
Abstract
:1. Introduction
2.2. Structure Elucidation
2.3. Discussion
3. Materials and Methods
3.1. General Experimental Procedures
3.2. Plant Materials
3.3. Extraction and Isolation
3.4. Chiral HPLC Analyses of Compounds 4 and 5
3.5. Calculation of ECD Spectra
3.6. Compound Data
- Compound 1
- Compound 2
- Compound 3
- Compound 4
- Compound 5
- Compound 14
- Compound 17
- Compound 21
- Compound 25
- Compound 26
- Compound 31
- Compound 32
- Compound 34
- Compound 36
- Compound 39
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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1 | 2 | 3 | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Position | δH | (mult., J in Hz) | δC | Position | δH | (mult., J in Hz) | δC | Position | δH | (mult., J in Hz) | δC |
2, 2′ | 5.00 | (1H, br s) | 92.9 | 2 | 5.04 | (1H, br s) | 92.2 | 2 | 4.97 | (1H, br s) | 91.86 |
3, 3′ | 5.34 | (1H, br s) | 77.7 | 3 | 5.21 | (1H, br s) | 76.3 | 3 | 5.06 | (1H, br s) | 76.22 |
4, 4′ | 119.2 | 4 | 128.1 | 4 | 126.31 | ||||||
5, 5′ | 153.4 | 5 | 148.8 | 5 | 149.28 | ||||||
6, 6′ | 130.3 | 6 | 6.91 | (1H, d, 8.8) | 122.1 | 6 | 6.76 | (1H, d, 8.8) | 118.89 | ||
7, 7′ | 7.14 | (1H, s) | 119.8 | 7 | 7.03 | (1H, d, 8.8) | 115.5 | 7 | 6.88 | (1H, d, 8.8) | 114.94 |
8, 8′ | 153.4 | 8 | 157.2 | 8 | 156.35 | ||||||
9, 9′ | 126.6 | 9 | 130.3 | 9 | 129.56 | ||||||
10, 10′ | 141.1 | 10 | 141.4 | 10 | 141.24 (a) | ||||||
11, 11′ | 5.10 | (1H, s) | 112.6 | 11 | 5.10 | (1H, s) | 112.0 | 11 | 5.04 | (1H, s) | 112.14 |
4.94 | (1H, s) | 4.92 | (1H, s) | 4.88 | (1H, s) | ||||||
12, 12′ | 1.79 | (3H, s) | 17.8 | 12 | 1.78 | (3H, s) | 17.6 | 12 | 1.72 | (3H, s) | 17.51 |
13, 13′ | 204.6 | 13 | 202.0 | 13 | 202.48 | ||||||
14, 14′ | 2.88 | (3H, s) | 31.1 | 14 | 2.69 | (3H, s) | 32.1 | 14 | 2.49 | (3H, s) | 32.23 |
3-OH, 3′-OH | 2.84 | (1H, br s) | 3-OH | 4.37 | (1H, br s) | 3-OH | 4.46 | (1H, d, 1.2) | |||
5-OH, 5′-OH | 11.72 | (1H, s) | 2′ | 4.95 | (1H, br s) | 93.0 | 2′ | 5.06 | (1H, br s) | 92.72 | |
3′ | 5.29 | (1H, dd, 7.1, 2.6) | 77.5 | 3′ | 5.24 | (1H, dd, 3.4, 1.7) | 75.98 | ||||
4′ | 119.2 | 4′ | 130.41 | ||||||||
5′ | 148.0 | 5′ | 147.93 | ||||||||
6′ | 147.2 | 6′ | 139.88 | ||||||||
7′ | 6.66 | (1H, s) | 106.4 | 7′ | 6.81 | (1H, s) | 107.59 | ||||
8′ | 153.0 | 8′ | 157.70 | ||||||||
9′ | 120.6 | 9′ | 126.03 | ||||||||
10′ | 141.0 | 10′ | 141.09 | ||||||||
11′ | 5.04 | (1H, s) | 112.5 | 11′ | 5.13 | (1H, s) | 112.23 | ||||
4.92 | (1H, s) | 4.96 | (1H, s) | ||||||||
12′ | 1.75 | (3H, s) | 17.7 | 12′ | 1.82 | (3H, s) | 17.74 | ||||
13′ | 203.6 | 13′ | 201.64 | ||||||||
14′ | 2.86 | (3H, s) | 31.3 | 14′ | 2.67 | (3H, s) | 30.98 | ||||
3′-OH | 2.93 | (1H, d, 7.1) | 3′-OH | 4.32 | (1H, d, 1.7) | ||||||
5′-OH | 10.49 | (1H, s) | 2″ | 4.91 | (1H, br s) | 93.22 | |||||
3″ | 5.14 | (1H, dd, 9.3, 2.4) | 77.28 | ||||||||
4″ | 118.39 | ||||||||||
5″ | 146.83 | ||||||||||
6″ | 146.83 | ||||||||||
7″ | 6.58 | (1H, s) | 104.86 | ||||||||
8″ | 152.60 | ||||||||||
9″ | 120.32 | ||||||||||
10″ | 141.09 (a) | ||||||||||
11″ | 4.98 | (1H, s) | 112.06 | ||||||||
4.87 | (1H, s) | ||||||||||
12″ | 1.71 | (3H, s) | 17.67 | ||||||||
13″ | 204.18 | ||||||||||
14″ | 2.78 | (3H, s) | 32.22 | ||||||||
3″-OH | 4.04 | (1H, d, 9.3) | |||||||||
5″-OH | 11.25 | (1H, s) |
4 | 5 | ||||||
---|---|---|---|---|---|---|---|
Position | δH | (mult., J in Hz) | δC | Position | δH | (mult., J in Hz) | δC |
2 | 160.2 | 2 | 161.7 | ||||
3 | 6.31 | (1H, d, 0.8) | 102.3 | 3 | 6.35 | (1H, s) | 99.0 |
4 | 7.70 | (1H, s) | 123.5 | 4 | 6.94 | (1H, s) | 106.5 |
5 | 116.8 | 5 | 158.7 | ||||
6 | 160.8 | 6 | 115.4 | ||||
7 | 6.79 | (1H, br s) | 99.1 | 7 | 7.70 | (1H, s) | 111.0 |
8 | 159.2 | 8 | 147.3 | ||||
9 | 120.8 | 9 | 137.5 | ||||
10 | 84.6 | 10 | 104.7 | ||||
11 | 2.84 | (1H, dd, 13.2, 1.2) | 43.1 | 11 | 7.37 | (1H, s) | 144.4 |
2.45 | (1H, dd, 13.2, 8.8) | 12 | 2.82 | (1H, dddd, 16.2, 11.2, 6.0, 1.8) | 18.9 | ||
12 | 1.74 | (3H, s) | 27.9 | 2.44 | (1H, dddd, 16.2, 5.4, 2.6, 1.0) | ||
13 | 204.0 | 13 | 203.4 | ||||
14 | 2.64 | (3H, s) | 26.9 | 14 | 2.66 | (3H, s) | 26.7 |
6-OH | 12.42 | (1H, s) | 5-OH | 12.26 | (1H, s) | ||
2′ | 122.8 | 1′ | 129.6 | ||||
3′ | 3.87 | (1H, d, 8.8) | 49.8 | 2′ | 7.47 | (1H, d, 1.9) | 110.0 |
4′ | 7.30 | (1H, d, 1.0) | 126.0 | 3′ | 146.7 | ||
5′ | 113.9 | 4′ | 151.6 | ||||
6′ | 165.9 | 5′ | 108.1 | ||||
7′ | 6.17 | (1H, s) | 97.9 | 6′ | 7.58 | (1H, d, 1.9) | 127.1 |
8′ | 165.5 | 7′ | 78.4 | ||||
9′ | 120.9 | 8′ | 94.8 | ||||
10′ | 141.7 | 9′ | 71.9 | ||||
11′ | 5.46 | (1H, s) | 113.8 | 10′ | 2.29 | (1H, ddd, 13.5, 6.0, 2.6) | 33.2 |
5.10 | (1H, t, 1.5) | 2.02 | (1H, ddd, 13.5, 11.2, 5.4) | ||||
12′ | 1.86 | (3H, s) | 18.2 | 11′ | 1.79 | (3H, s) | 28.1 |
13′ | 201.8 | 12′ | 196.1 | ||||
14′ | 2.44 | (3H, s) | 26.1 | 13′ | 2.53 | (3H, s) | 26.2 |
5′-OH | 12.76 | (1H, s) | 3′-OCH3 | 3.92 | (3H, s) | 56.3 | |
4′-OH | 6.28 | (1H, s) |
14 | 17 | 21 | |||||||
---|---|---|---|---|---|---|---|---|---|
Position | δH | (mult., J in Hz) | δC | δH | (mult., J in Hz) | δC | δH | (mult., J in Hz) | δC |
2 | 5.14 | (1H, d, 6.4) | 89.2 | 160.6 | 5.47 | (1H, d, 6.1) | 88.4 | ||
3 | 6.26 | (1H, d, 6.4) | 72.2 | 6.64 | (1H, d, 1.0) | 102.5 | 5.67 | (1H, d, 6.1) | 81.9 |
4 | 7.81 | (1H, s) | 130.0 | 7.93 | (1H, s) | 123.7 | 7.81 | (1H, s) | 129.2 |
5 | 114.7 | 117.0 | 114.8 | ||||||
6 | 166.7 | 161.1 | 167.0 | ||||||
7 | 6.46 | (1H, s) | 98.9 | 6.99 | (1H, br s) | 99.8 | 6.38 | (1H, s) | 98.5 |
8 | 166.7 | 159.5 | 166.8 | ||||||
9 | 117.8 | 120.8 | 118.3 | ||||||
10 | 138.0 | 71.3 | 145.3 | ||||||
11 | 5.20 | (1H, d, 1.0) | 114.7 | 4.53 | (1H, d, 11.5) | 69.7 | 4.36 | (1H, d, 12.5) | 69.2 |
5.12 | (1H, d, 1.0) | 4.38 | (1H, d, 11.5) | 4.22 | (1H, d, 12.5) | ||||
12 | 1.81 | (3H, s) | 19.2 | 1.67 | (3H, s) | 23.9 | 5.56 | (1H, s) | 112.9 |
5.38 | (1H, s) | ||||||||
13 | 202.7 | 204.0 | 202.5 | ||||||
14 | 2.57 | (3H, s) | 26.4 | 2.69 | (3H, s) | 26.9 | 2.58 | (3H, s) | 26.3 |
1′ | 174.1 | 167.9 | |||||||
2′ | 2.31 | (2H, q, 7.6) | 27.7 | 127.1 | |||||
3′ | 1.12 | (3H, t, 7.6) | 9.0 | 6.09 | (1H, qq, 7.3, 1.4) | 139.5 | |||
4′ | 1.89 | (3H, dq, 7.3, 1.4) | 15.8 | ||||||
5′ | 1.83 | (3H, quint, 1.4) | 20.5 | ||||||
6-OH | 13.04 | (1H, s) | 12.46 | (1H, s) | 12.99 | (1H, s) |
25 | 26 | 31 | 32 | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
Position | δH | (mult., J in Hz) | δC | δH | (mult., J in Hz) | δC | δH | (mult., J in Hz) | δC | δH | (mult., J in Hz) | δC |
2 | 166.8 | 165.7 | 162.0 | 154.2 | ||||||||
3 | 6.46 | (1H, s) | 102.8 | 6.42 | (1H, s) | 102.6 | 6.70 | (1H, s) | 102.7 | 7.56 | (1H, s) | 112.9 |
4 | 7.01 | (1H, s) | 107.4 | 7.01 | (1H, s) | 107.5 | 7.80 | (1H, d, 1.5) | 115.9 | 7.93 | (1H, d, 1.5) | 117.4 |
5 | 158.4 | 158.4 | 133.8 | 134.7 | ||||||||
6 | 115.8 | 115.9 | 7.48 | (1H, d, 1.5) | 105.5 | 7.62 | (1H, d, 1.5) | 108.0 | ||||
7 | 7.78 | (1H, s) | 111.8 | 7.78 | (1H, s) | 111.8 | 145.3 | 146.2 | ||||
8 | 147.8 | 147.7 | 146.8 | 147.8 | ||||||||
9 | 136.7 | 136.7 | 129.4 | 128.3 | ||||||||
10 | 3.18 | (1H, sext, 6.5) | 36.9 | 3.32 | (1H, sext, 6.8) | 33.7 | 5.06 | (1H, m) | 64.0 | 188.6 | ||
11 | 3.88 | (2H, m) | 66.0 | 4.36 | (1H, dd, 11.0, 6.8) | 66.3 | ||||||
4.27 | (1H, dd, 11.0, 6.3) | |||||||||||
12 | 1.39 | (3H, d, 7.1) | 14.9 | 1.39 | (3H, d, 7.1) | 15.4 | 1.66 | (3H, d, 6.6) | 21.4 | 2.66 | (3H, s) | 26.7 |
13 | 203.7 | 203.8 | 197.6 | 197.1 | ||||||||
14 | 2.68 | (3H, s) | 26.7 | 2.68 | (3H, s) | 26.7 | 2.66 | (3H, s) | 26.6 | 2.68 | (3H, s) | 26.6 |
1′ | 170.9 | |||||||||||
2′ | 2.05 | (3H, s) | 20.9 | |||||||||
5-OH | 12.16 | (1H, s) | 12.16 | (1H, s) | ||||||||
7-OCH3 | 4.06 | (3H, s) | 56.1 | 4.08 | (3H, s) | 56.2 | ||||||
10-OH | 2.18 | (1H, d, 4.9) |
34 | 36 (a) | 39 | ||||||||
---|---|---|---|---|---|---|---|---|---|---|
Position | δH | (mult., J in Hz) | δC | δH | (mult., J in Hz) | δH (Major/Minor) | (mult., J in Hz) | δC (Major/Minor) | ||
1 | 141.60 | |||||||||
2 | 5.13 | (1H, d, 2.8) | 92.1 | 5.04 | (1H, d, 4.0) | 6.761 | (1H, d, 0.5) | 111.67 | ||
3 | 6.17 | (1H, d, 2.8) | 77.3 | 5.22 | (1H, dd, 7.8, 4.0) | 158.47 | ||||
4 | 7.62 | (1H, d, 1.5) | 120.7 | 7.65 | (1H, d, 1.5) | 127.58 | ||||
5 | N.D. (b) | 7.222 | (1H, d, 7.6) | 122.68 | ||||||
6 | 7.59 | (1H, d, 1.5) | 113.0 | 7.57 | (1H, d, 1.5) | 6.848 | (1H, dd, 7.6, 0.5) | 123.07 | ||
7 | 144.8 | 2.353 | (3H, s) | 21.72 | ||||||
8 | 154.0 | 79.73 | ||||||||
9 | N.D. (b) | 6.506 | (1H, s) | 104.85/104.80 | ||||||
10 | 140.5 | 1.626 | (3H, s) | 20.12 | ||||||
11 | 5.10 | (1H, s) | 114.1 | 5.13 | (1H, d, 0.8) | |||||
4.98 | (1H, s) | 4.97 | (1H, d, 0.8) | |||||||
12 | 1.76 | (3H, s) | 17.5 | 1.76 | (3H, s) | |||||
13 | 196.4 | |||||||||
14 | 2.56 | (3H, s) | 26.4 | 2.58 | (3H, s) | |||||
1′ | 176.8 | 175.28 | ||||||||
2′ | 2.57 | (1H, sept, 7.1) | 33.9 | 2.407/2.398 | (1H, sext, 7.0) | 41.02/40.97 | ||||
3′ | 1.20 | (3H, d, 7.1) | 18.9 | 1.688 | (1H, m) | 26.49/26.35 | ||||
1.498 | (1H, m) | |||||||||
4′ | 1.17 | (3H, d, 7.1) | 18.8 | 0.913/0.907 | (3H, t, 7.0) | 11.42 | ||||
5′ | 1.157/1.164 | (3H, d, 7.0) | 16.07/16.38 | |||||||
3-OH | 2.16 | (1H, d, 7.8) | ||||||||
7-OCH3 | 3.96 | (3H, s) | 56.2 | 3.96 | (3H, s) | |||||
8-OH | 2.033/2.036 | (1H, s) |
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Hu, Y.; Saito, Y.; Matsuo, Y.; Gong, X.; Tanaka, T. New Benzofuran Oligomers from the Roots of Eupatorium heterophyllum Collected in China. Molecules 2022, 27, 8856. https://doi.org/10.3390/molecules27248856
Hu Y, Saito Y, Matsuo Y, Gong X, Tanaka T. New Benzofuran Oligomers from the Roots of Eupatorium heterophyllum Collected in China. Molecules. 2022; 27(24):8856. https://doi.org/10.3390/molecules27248856
Chicago/Turabian StyleHu, Yiming, Yoshinori Saito, Yosuke Matsuo, Xun Gong, and Takashi Tanaka. 2022. "New Benzofuran Oligomers from the Roots of Eupatorium heterophyllum Collected in China" Molecules 27, no. 24: 8856. https://doi.org/10.3390/molecules27248856