Table 1.
13C and 1H NMR spectroscopic data for bromophycoic acids A-E (1–5) (500 MHz; in DMSO-d6 for 1–4; in CDCl3 for 5). 13C NMR chemical shifts for 2 and 4 were inferred by DEPT-135, HSQC, and HMBC experiments rather than by 13C NMR spectra.
| 1
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2
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3
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4
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5
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| No. | δC | δH, (JH,H) | δC | δH, (JH,H) | δC | δH, (JH,H) | δC | δH, (JH,H) | δC | δH, (JH,H) | |||||
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| 1 | 167.3 | 167.5 | 167.6 | 167.5 | 170.7 | ||||||||||
| 2 | 122.6 | 123.2 | 124.5 | 124.2 | 120.2 | ||||||||||
| 3 | 126.1 | 7.72 | s | 126.1 | 7.71 | s | 125.9 | 7.70 | s | 126.0 | 7.70 | s | 132.3 | 7.82 | s |
| 4 | 128.4 | 128.4 | 127.9 | 128.0 | 121.1 | ||||||||||
| 5 | 28.8 | 3.07 (15.7, 8,4) | dd | 28.9 | 3.03 (15.8, 8.7) | dd | 28.8 | 3.02 (16.1, 8.7) | dd | 28.8 | 3.05 (15.6, 9.3) | dd | 29.1 | 2.47 (16.5, 12.3) | dd |
| 3.22 (15.7, 9.6) | dd | 3.18 (15.8, 9.2) | dd | 3.19 (15.7, 9.5) | dd | 3.20 (15.5, 8.2) | dd | 2.62 (16.7, 5.3) | dd | ||||||
| 6 | 86.1 | 5.13 (8.8) | t | 86.1 | 5.13 (9.0) | t | 85.6 | 5.11 (9.1) | t | 86.0 | 5.10 (9.0) | t | 33.0 | 2.11 | m |
| 7 | 71.0 | 71.2 | 71.0 | 71.0 | 83.1 | ||||||||||
| 8 | 54.2 | 1.25 | m | 54.1 | 1.20 | m | 54.1 | 1.16 | m | 54.0 | 1.25 | m | 41.9 | ||
| 1.50 (13.6) | d | 1.48 (11.0) | d | 1.48 (13.6) | d | 1.49 | m | ||||||||
| 9 | 34.0 | 34.1 | 34.0 | 34.1 | 33.0 | 1.72 | m | ||||||||
| 1.83 | m | ||||||||||||||
| 10 | 42.7 | 1.28 | m | 42.7 | 1.17 | m | 42.7 | 1.15 | m | 42.4 | 1.33 | m | 30.6 | 2.22 (13.3, 3.7) | dd |
| 1.36 (14.5) | d | 1.36 (13.2) | d | 2.32 (12.7, 12.7, 12.7, 3.3) | dddd | ||||||||||
| 11 | 30.4 | 2.00 | m | 30.3 | 2.01 | m | 30.1 | 2.00 | m | 30.3 | 2.00 | m | 64.0 | 4.29 (12.6, 4.2) | dd |
| 2.24 (12.6, 12.6, 12.6, 2.8) | dddd | 2.22 (12.1, 12.1, 12.1, 2.7) | dddd | 2.22 (12.7, 12.7, 12.7, 2.4) | dddd | 2.23 (12.9, 12.9, 12.9, 2.7) | dddd | ||||||||
| 12 | 65.2 | 4.49 (12.2, 4.1) | dd | 65.5 | 4.29 (12.5, 4.1) | dd | 65.5 | 4.33 (12.5, 4.4) | dd | 64.8 | 4.51 (12.3, 4.4) | dd | 41.8 | ||
| 13 | 41.1 | 41.9 | 42.3 | 40.9 | 39.6 | 1.41 (14.2, 4.7) | m | ||||||||
| 1.57 (14.2, 4.7) | dd | ||||||||||||||
| 14 | 39.5 | 1.37 | m | 41.2 | 2.07 | m | 41.2 | 2.11 | m | 34.0 | 1.60 | m | 21.3 | 1.80 | m |
| 1.95 | m | ||||||||||||||
| 15 | 20.7 | 1.75 | m | 119.3 | 5.47 (15.4, 7.3, 7.3) | ddd | 123.3 | 5.50 (15.7, 7.7, 7.7) | ddd | 30.4 | 2.41 | m | 123.9 | 5.12 (6.8) | t |
| 1.93 | m | 2.81 | m | ||||||||||||
| 16 | 124.1 | 5.08 (15.4, 7.2) | dd | 143.1 | 5.64 (15.4) | d | 138.5 | 5.65 (15.7) | d | 202.0 | 131.8 | ||||
| 17 | 130.8 | 69.1 | 80.0 | 143.4 | 25.8 | 1.71 | s | ||||||||
| 18 | 25.5 | 1.66 | s | 30.1 | 1.19 | s | 24.4 | 1.26 | s | 125.6 | 5.90 | s | 129.9 | 7.83 | m |
| 6.17 | s | ||||||||||||||
| 19 | 130.2 | 7.68 (8.0) | d | 130.2 | 7.68 (8.7) | d | 129.9 | 7.67 (8.2) | d | 129.9 | 7.66 (8.3) | d | 117.3 | 6.79 (8.4) | d |
| 20 | 108.3 | 6.75 (8.1) | d | 108.3 | 6.73 (8.4) | d | 107.7 | 6.70 (8.4) | d | 108.1 | 6.71 (8.4) | d | 159.0 | ||
| 21 | 163.6 | 163.5 | 162.9 | 163.1 | 29.4 | 1.18 | m | ||||||||
| 1.85 | m | ||||||||||||||
| 22 | 36.3 | 1.32 | m | 36.3 | 1.27 | m | 36.2 | 1.25 | m | 36.1 | 1.32 | m | 22.4 | 1.63 | m |
| 2.34 | m | 2.31 | m | 2.31 | m | 2.30 | m | ||||||||
| 23 | 20.0 | 1.48 | m | 19.8 | 1.41 | m | 19.7 | 1.42 | m | 19.8 | 1.43 | m | 42.5 | 1.69 | m |
| 1.51 | m | ||||||||||||||
| 1.59 | m | 1.60 | m | ||||||||||||
| 24 | 47.5 | 1.31 | m | 48.0 | 1.18 | m | 48.1 | 1.15 | m | 47.2 | 13.3 | 1.19 | s | ||
| 25 | 21.1 | 0.96 | s | 20.9 | 0.96 | s | 20.8 | 0.96 | s | 21.0 | 0.96 | s | 15.0 | 1.15 | s |
| 26 | 19.1 | 0.83 | s | 18.7 | 0.85 | s | 18.5 | 0.86 | s | 19.0 | 0.87 | s | 19.5 | 1.01 | s |
| 27 | 17.4 | 1.60 | s | 30.4 | 1.17 | s | 25.0 | 1.23 | s | 17.3 | 1.78 | s | 17.7 | 1.65 | s |