Cordyanhydrides A and B. Two unique anhydrides from the insect pathogenic fungus Cordyceps pseudomilitaris BCC 1620

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Compound 1: colorless oil; [α]D26 −1° (c 0.94, CHCl3); UV (MeOH) λmax (log ε) 209 (4.26), 262 (3.98), 3.11 (3.85); HR-FABMS m/z 391.1404 (calcd for C20H23O8 [M+H]+ 391.1393); EIMS m/z 390 [M]+, 373, 372, 207, 166.

Compound 2: colorless amorphous solid; [α]D25 +1° (c 1.15, CHCl3); UV (MeOH) λmax (log ε) 209 (4.31), 262 (4.20); IR (KBr) νmax 1825, 1765 (s), 1715, 1650, 1275, 1225, 925, 750 cm−1; 1H NMR (CDCl3, 400 MHz) δ 7.9 (1H, brs, -CO2H), 7.28 (1H, dt, J=15.8, 6.7 Hz, H-17), 6.23 (1H, d, J=15.8 Hz, H-16), 2.77 (4H, m, H-2 and H-3), 2.58–2.53 (4H, m, H-6a, H-8a, H-11a and H-13a), 2.42–2.39 (4H, m, H-6b, H-8b, H-11b and H-13b), 2.35 (1H, m, H-18), 2.24 (2H, m, H-7 and H-12), 1.34 (4H, m, H-26 and H-18), 1.12 (3H, t, J=7.4 Hz, H-19), 0.97 (6H, t, J=7.3 Hz, H-27 and H-29);13C NMR (CDCl3, 100 MHz) δ 176.8 (s, C-1), 166.3 (s, C-24), 165.6 (s), 165.5 (s), 165.5 (s), 165.0 (s), 164.0 (s, C-25), 150.6 (d, C-17), 144.3 (s), 144.2 (s), 144.0 (s), 143.6 (s), 138.5 (s, C-15), 136.6 (s, C-14), 115.9 (d, C-16), 37.9 (d), 37.7 (d), 30.6 (t, C-2), 28.9 (t), 28.8 (t), 28.6 (t), 28.1 (t, C-13), 27.4 (t, C-18), 26.7 (t), 26.6 (t), 19.7 (t, C-3), 12.3 (q, C-19), 10.6 (q, C-27), 10.6 (q, C-29). Anal. C 62.59%, H 5.83%, calcd for C29H32O11, C 62.58%, H 5.80%.

Compound 3: colorless oil; IR (KBr) νmax 1732 (br), 1635, 1436, 757 cm−1; 1H NMR (CDCl3, 400 MHz) δ 6.31 (1H, dt, J=15.8, 1.6 Hz, H-11), 6.01 (1H, dt, J=15.8, 6.6 Hz, H-12), 3.84 (3H, s, 18-OCH3), 3.75 (3H, s, 15-OCH3), 3.73 (3H, s, 16-OCH3), 3.72 (3H, s, 17-OCH3), 3.68 (3H, s, 1-OCH3), 2.69 (2H, m, H-3), 2.45 (2H, m, H-2), 2.44–2.42 (2H, m, H-6a and H-8a), 2.37 (1H, dd, J=13.7, 6.5 Hz, H-6b), 2.31 (1H, dd, J=14.0, 6.9 Hz, H-8b), 2.24 (2H, m, H-13), 1.63 (1H, m, H-7), 1.31 (2H, m, H-19), 1.05 (3H, t, J=7.5 Hz, H-14), 0.91 (3H, t, J=7.3 Hz, H-20); 13C NMR (CDCl3, 100 MHz) δ 172.5 (s, C-1), 169.3 (s, C-18), 168.8 (s, C-17), 168.5 (s, C-15), 167.5 (s, C-16), 143.4 (d, C-12), 142.8 (s, C-10), 138.2 (s, C-5), 52.3 (q, 17-OCH3), 52.3 (q, 18-OCH3), 52.2 (q, 15-OCH3), 52.2 (q, 16-OCH3), 51.8 (q, 1-OCH3), 39.6 (d, C-7), 33.5 (t, C-8), 32.1 (t, C-2), 31.2 (t, C-6), 26.6 (t, C-13), 26.0 (t, C-19), 25.0 (t, C-3), 12.9 (q, C-14), 11.1 (q, C-20). Anal. C 60.42%, H 7.33%, calcd for C25H36O10, C 60.47%, H 7.31%.

Compound 4: colorless oil; IR (KBr) νmax 1732 (br), 1636, 1437, 792 cm−1; 1H NMR (CDCl3, 400 MHz) δ 6.31 (1H, d, J=15.8 Hz, H-16), 6.01 (1H, dt, J=15.7, 6.5 Hz, H-17), 3.75 (3H, s), 3.74–3.73 (12H, m), 3.71 (3H, s), 3.68 (3H, s, 1-OCH3), 2.68 (2H, t, J=7.7 Hz, H-3), 2.44 (2H, t, J=7.7 Hz, H-2), 2.40–2.25 (8H, m, H-6, H-8, H-11 and H-13), 2.24 (2H, m, H-18), 1.54 (2H, m, H-7 and H-12), 1.29 (4H, m, H-26 and H-28), 1.03 (3H, t, J=7.5 Hz, H-19), 0.90 (3H, t, J=7.3 Hz, H-29), 0.88 (3H, t, J=7.5 Hz, H-27); 13C NMR (CDCl3, 100 MHz) δ 172.5 (s, C-1), 169.2 (s), 169.1 (s), 168.9 (s), 168.7 (s), 168.1 (s, C-20), 167.4 (s), 143.3 (d, C-17), 142.7 (s, C-15), 139.0 (s), 138.9 (s), 137.1 (s), 136.0 (s), 127.3 (s, C-14), 122.6 (d, C-16), 52.2 (q), 52.2 (q), 52.1 (q), 52.1 (q), 52.0 (q), 52.0 (q), 51.7 (q, 1-OCH3), 39.8 (d), 38.0 (d), 33.9 (t), 33.6 (t), 33.3 (t), 32.1 (t, C-2), 31.0 (t), 26.5 (t, C-18), 25.7 (t), 25.6 (t), 24.6 (t, C-3), 12.9 (q, C-19), 11.0 (q), 10.9 (q). Anal. C 61.04%, H 7.39%, calcd for C36H52O14, C 61.00%, H 7.39%.

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