A R T I C L E S
Pirrung et al.
(20 mL), neutralized with sulfuric acid (10% aq, about 3 mL) to pH 2,
extracted with ethyl acetate (20 mL × 2), washed with brine (20 mL),
dried with sodium sulfate, and purified by flash chromatography (oxalic
acid-coated silica gel, ethyl acetate:hexanes 3:7). The title compound
132.7, 130.5, 127.7, 127.3, 127.2, 127.0, 124.5, 122.4, 120.9, 120.7,
119.9, 119.5, 118.7, 118.4, 111.1, 110.8, 105.4, 100.6, 39.3, 26.8, 25.2,
21.1, 17.3. IR (KBr): 3410, 3331, 2964, 2923, 1636, 1437, 1341, 1304,
1243, 1127 cm-1. HRMS: calcd for C33H32N2O2 520.2362, found
520.2355.
1
was obtained as a red solid (28 mg, 60%). H NMR (acetone-d6): δ
10.43 (1H, s), 10.07 (1H, s), 9.34 (2H, br s), 7.64-6.92 (8H, m), 6.18
(1H, dd, J ) 17.4, 10.8 Hz), 5.50-5.46 (1H, m), 5.10 (1H, d, J )
17.4 Hz), 5.01 (1H, d, J ) 10.8 Hz), 3.65 (2H, d, J ) 6.9 Hz), 1.78
(3H, s), 1.76 (3H, s), 1.52 (6H, s). 13C NMR (acetone-d6): δ 146.0,
142.6, 135.8, 135.2, 132.7, 129.2, 127.4, 127.0, 124.5, 122.4, 121.2,
120.9, 119.9, 119.5, 119.0, 118.9, 112.5, 111.6, 110.9, 110.8, 105.3,
100.8, 39.4, 27.0, 25.4, 17.5.
2-[2-(1,1-Dimethylallyl)-1H-indol-3-yl]-3,6-dihydroxy-5-[1-meth-
yl-7-(3-methylbut-2-enyl)-1H-indol-3-yl]-[1,4]benzoquinone (26{6}).
This compound was synthesized analogously to 26{8}. Yield: 70%.
1
Mp: 109-110 °C. H NMR (acetone-d6): δ 10.10 (1H, s), 9.43 (2H,
s), 7.42-6.92 (8H, m), 6.17 (1H, dd, J ) 17.2, 10.5 Hz), 5.36 (1H, t,
J ) 6.3 Hz), 5.13-4.98 (2H, m), 4.12 (1H, s), 3.85 (2H, d, J ) 6.3
Hz), 1.78 (3H, s), 1.76 (3H, s), 1.52 (6H, s). 13C NMR (acetone-d6):
δ 146.0, 142.6, 135.8, 135.1, 133.3, 131.7, 129.2, 129.0, 125.4, 124.8,
123.2, 121.2, 120.4, 119.5, 119.0, 118.9, 112.6, 111.3, 110.9, 110.8,
103.6, 100.8, 39.4, 36.6, 31.5, 27.0, 25.3, 17.7. IR (KBr): 3419, 3322,
2968, 2927, 1636, 1541, 1457, 1340, 1245, 990 cm-1. HRMS: calcd
for C33H32N2O2 520.2362, found 520.2357.
2-[2-(1,1-Dimethylallyl)-1-methyl-1H-indol-3-yl]-3,6-dihydroxy-
5-[7-(3-methylbut-2-enyl)-1H-indol-3-yl]-[1,4]benzoquinone (26{1}).
1
Yield: 47%. Mp: 114-115 °C. H NMR (acetone-d6): δ 10.47 (1H,
s), 9.49 (2H, s), 7.64-6.96 (8H, m), 6.24 (1H, dd, J ) 17.6, 10.5 Hz),
5.48 (1H, t, J ) 6.9 Hz), 5.16-5.10 (2H, m), 3.84 (3H, s), 3.65 (2H,
d, J ) 6.9 Hz), 1.78 (3H, s), 1.76 (3H, s), 1.56 (6H, s). 13C NMR
(acetone-d6): δ 147.3, 142.6, 138.1, 135.2, 132.7, 128.2, 127.4, 127.3,
127.0, 124.5, 122.4, 121.6, 120.9, 120.0, 119.5, 119.2, 118.9, 113.5,
111.8, 109.0, 105.4, 102.1, 40.3, 32.8, 28.0, 25.4, 17.4. IR (KBr): 3402,
1685, 1670, 1654, 1560, 1508, 1473, 1458, 1210, 737 cm-1. HRMS:
calcd for C33H32N2O2 520.2362, found 520.2366.
2-[2-(1,1-Dimethylallyl)-1H-indol-3-yl]-3,6-dihydroxy-5-[2-meth-
yl-7-(3-methylbut-2-enyl)-1H-indol-3-yl]-[1,4]benzoquinone (26{7}).
1
Yield: 82%. Mp: 214-215 °C. H NMR (acetone-d6): δ 10.12 (1H,
s), 10.09 (1H, s), 7.37-6.86 (7H, m), 6.18 (1H, dd, J ) 17.8, 9.3 Hz),
5.51-5.46 (1H, m), 5.14-4.99 (2H, m), 3.59 (2H, d, J ) 6.9 Hz),
2.83 and 2.37 (1H, s), 1.76 (6H, s), 1.52 (6H, s). 13C NMR (acetone-
d6): δ 169.6, 168.5, 146.1, 142.6, 135.8, 135.2, 134.8, 132.4, 129.2,
128.6, 123.7, 122.6, 121.1, 120.0, 119.3, 119.0, 118.0, 117.6, 112.6,
110.8, 103.1, 101.0, 39.4, 27.0, 25.4, 17.4, 12.9. IR (KBr): 3402, 3330,
2970, 1701, 1654, 1637, 1560, 1459, 1340, 1283 cm-1. HRMS: calcd
for C33H32N2O2 520.2362, found 520.2350.
2-[2-(1,1-Dimethylallyl)-7-methyl-1H-indol-3-yl]-3,6-dihydroxy-
5-[7-(3-methylbut-2-enyl)-1H-indol-3-yl]-[1,4]benzoquinone (26{2}).
1
Yield: 45%. Mp: 135-136 °C. H NMR (acetone-d6): δ 10.46 (1H,
s), 9.70 (1H, s), 9.41 (1H, s), 7.64-6.84 (7H, m), 6.20 (1H, dd, J )
17.4, 10.5 Hz), 5.48 (1H, d, J ) 7.2 Hz), 5.11-4.97 (2H, m), 3.65
(2H, d, J ) 6.9 Hz), 2.48 (3H, s), 1.78 (3H, s), 1.76 (3H, s), 1.54 (6H,
s). 13C NMR (acetone-d6): δ 146.1, 142.5, 135.2, 132.7, 128.8, 127.7,
127.3, 127.0, 124.5, 122.4, 122.1, 120.9, 120.2, 119.8, 119.5, 119.3,
116.7, 112.7, 111.2, 110.8, 105.4, 101.5, 39.5, 29.8, 27.0, 25.4, 17.5,
16.6. IR (KBr): 3378, 3338, 2969, 1693, 1637, 1533, 1438, 1340, 1282,
1261 cm-1. HRMS: calcd for C33H32N2O2 520.2362, found 520.2358.
2-[2-(1,1-Dimethylallyl)-6-methyl-1H-indol-3-yl]-3,6-dihydroxy-
5-[7-(3-methylbut-2-enyl)-1H-indol-3-yl]-[1,4]benzoquinone (26{3}).
2-[2-(1,1-Dimethylallyl)-1H-indol-3-yl]-3,6-dihydroxy-5-[4-meth-
yl-7-(3-methylbut-2-enyl)-1H-indol-3-yl]-[1,4]benzoquinone (26{8}).
This compound was synthesized analogously to 26{7}, except that for
the hydrolysis, the sodium hydroxide solution was added over 30 min
1
via a syringe pump. Yield: 15% for two steps. Mp: 75-76 °C. H
NMR (acetone-d6): δ 10.26 (1H, s), 10.14 and 10.09 (1H, s), 9.43
(2H, s), 7.35-6.73 (7H, m), 6.17 (1H, dd, J ) 13.0, 8.1 Hz), 5.49-
5.45 (1H, m), 5.13-4.96 (2H, m), 3.60 (2H, d, J ) 5.4 Hz), 2.46 and
2.43 (3H, s), 1.78 (3H, s), 1.76 (3H, s), 1.53 (6H, s). 13C NMR (acetone-
d6): δ 146.0, 145.9, 145.8, 142.6, 135.8, 135.6, 132.5, 129.1, 127.8,
125.4, 122.6, 122.4, 121.5, 121.2, 120.9, 119.5, 119.0, 118.6, 111.4,
111.0, 105.2, 100.8, 39.4, 27.0, 26.7, 25.4, 17.4. IR (KBr): 3402, 2923,
2852, 1654, 1608, 1458, 1274, 934, 914, 805 cm-1. HRMS: calcd for
C33H32N2O2 520.2362, found 520.2368.
1
Yield: 55%. Mp: 141-142 °C. H NMR (acetone-d6): δ 10.46 (1H,
s), 9.93 (1H, s), 9.40 (1H, s), 7.63-6.78 (7H, m), 6.16 (1H, dd, J )
17.6, 10.5 Hz), 5.52-5.46 (1H, m), 5.13-4.98 (2H, m), 3.65 (2H, d,
J ) 7.2 Hz), 2.38 (3H, s), 1.79 (3H, s), 1.76 (3H, s), 1.51 (6H, s). 13
C
NMR (acetone-d6): δ 146.1, 141.9, 136.2, 135.2, 132.7, 130.5, 127.3,
127.1, 127.0, 124.5, 122.4, 120.9, 120.7, 119.9, 119.5, 118.7, 112.7,
111.6, 110.8, 105.4, 100.6, 39.4, 29.8, 27.0, 25.4, 21.3, 17.5. IR
(KBr): 3402, 3337, 2969, 2915, 1700, 1636, 1458, 1437, 1340, 1282
cm-1. HRMS: calcd for C33H32N2O2 520.2362, found 520.2352.
2-[2-(1,1-Dimethylallyl)-5-methyl-1H-indol-3-yl]-3,6-dihydroxy-
5-[7-(3-methylbut-2-enyl)-1H-indol-3-yl]-[1,4]benzoquinone (26{4}).
2-[2-(1,1-Dimethylallyl)-1H-indol-3-yl]-3,6-dihydroxy-5-[5-meth-
yl-7-(3-methylbut-2-enyl)-1H-indol-3-yl]-[1,4]benzoquinone (26{9}).
This compound was synthesized analogously to 26{8}. Yield: 12%
for two steps. Mp: 129-130 °C. 1H NMR (acetone-d6): δ 10.34 (1H,
s), 10.09 (1H, s), 9.40 (2H, s), 7.58-6.82 (7H, m), 6.18 (1H, dd, J )
17.4, 10.5 Hz), 5.49-5.44 (1H, m), 5.14-4.99 (2H, m), 3.61 (2H, d,
1
Yield: 68%. Mp: 109-110 °C. H NMR (acetone-d6): δ 10.43 (1H,
s), 9.94 (1H, s), 9.36 (1H, s), 7.63-6.87 (7H, m), 6.16 (1H, dd, J )
17.4, 10.5 Hz), 5.48 (1H, t, J ) 6.9 Hz), 5.12-4.98 (2H, m), 3.65
(2H, d, J ) 6.9 Hz), 2.33 (3H, s), 1.78 (3H, s), 1.76 (3H, s), 1.51 (6H,
s). 13C NMR (acetone-d6): δ 146.1, 142.7, 135.2, 134.1, 132.7, 129.5,
127.8, 127.4, 127.0, 124.5, 123.0, 122.7, 122.4, 120.9, 119.9, 119.5,
118.6, 110.8, 110.6, 105.4, 103.6, 100.3, 39.4, 29.8, 27.0, 25.4, 21.1,
17.5. IR (KBr): 3413, 3339, 2967, 2915, 1653, 1636, 1437, 1341, 1304,
1244 cm-1. HRMS: calcd for C33H32N2O2 520.2362, found 520.2366.
2-[2-(1,1-Dimethylallyl)-4-methyl-1H-indol-3-yl]-3,6-dihydroxy-
5-[7-(3-methylbut-2-enyl)-1H-indol-3-yl]-[1,4]benzoquinone (26{5}).
This compound was synthesized analogously to DAQ B1, except that
25{5} was hydrolyzed immediately after preparation, without isolation/
characterization, after most of the solvent had been removed in vacuo.
Yield: 9% for two steps. Mp: 105-106 °C. 1H NMR (acetone-d6): δ
10.43 (1H, s), 9.90 (1H, s), 9.38 (2H, s), 7.63-6.78 (7H, m), 6.16
(1H, dd, J ) 13.2, 7.8 Hz), 5.48 (1H, t, J ) 5.4 Hz), 5.11-4.98 (2H,
m), 3.65 (2H, d, J ) 5.4 Hz), 2.38 (3H, s), 1.78 (3H, s), 1.76 (3H, s),
1.50 (6H, s). 13C NMR (acetone-d6): δ 146.2, 141.9, 136.2, 135.2,
J ) 7.2 Hz), 2.38 (3H, s), 1.78 (3H, s), 1.76 (3H, s), 1.53 (6H, s). 13
C
NMR (acetone-d6): δ 146.0, 142.6, 135.8, 133.6, 132.5, 129.2, 128.2,
127.4, 127.3, 124.2, 122.6, 122.5, 121.2, 119.6, 119.0, 112.4, 111.8,
111.2, 110.9, 110.8, 104.9, 100.8, 39.4, 29.8, 27.0, 25.4, 21.4, 17.5.
IR (KBr): 3413, 2966, 2922, 1653, 1636, 1458, 1341, 1302, 990, 918
cm-1. HRMS: calcd for C33H32N2O2 520.2362, found 520.2365.
2-[2-(1,1-Dimethylallyl)-1H-indol-3-yl]-3,6-dihydroxy-5-[6-meth-
yl-7-(3-methylbut-2-enyl)-1H-indol-3-yl]-[1,4]benzoquinone (26-
{10}). This compound was synthesized analogously to 26{8}. Yield:
14% for two steps. Mp: 179-180 °C. 1H NMR (acetone-d6): δ 10.32
(1H, s), 10.09 (1H, s), 9.40 (2H, s), 7.59-6.88 (7H, m), 6.12-6.12
(1H, m), 5.19-4.98 (3H, m), 3.64 (2H, d, J ) 6.6 Hz), 2.38 (3H, s),
1.84 (3H, s), 1.69 (3H, s), 1.52 (6H, s). 13C NMR (acetone-d6): δ 146.0,
142.6, 135.9, 135.8, 131.4, 129.2, 128.4, 127.1, 125.5, 122.8, 122.6,
122.3, 121.2, 119.6, 119.0, 118.9, 112.4, 111.8, 110.9, 110.8, 105.3,
100.8, 39.4, 27.1, 27.0, 25.3, 18.6, 17.6. IR (KBr): 3421, 3341, 2968,
1654, 1636, 1617, 1458, 1438, 1340, 1283 cm-1. HRMS: calcd for
C33H32N2O2 520.2362, found 520.2371.
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4622 J. AM. CHEM. SOC. VOL. 127, NO. 13, 2005