W. Steglich et al.
FULL PAPER
Tridentorubin (5): Red oil. Rf (TLC) = 0.67 (solvent system A),
orange spot, + NH3 no colour change. Rt (HPLC) = 45.73 min
J = 5.5 Hz, 1 H, 14Ј-H), 3.37 (dd, J = 15, 7.5 Hz, 1 H, 1Ј-HB),
4.82, 4.96 (each t, br., J ≈ 6.3 Hz, 1 H, 6Ј-H, 10Ј-H), 5.13 (t, br., J
≈ 7.7 Hz, 1 H, 2Ј-H), 6.34 (pseudo-q, J ≈ 1.1 Hz, 1 H, 6-H) ppm.
20
(system 1). [α]D = +1054 (c = 0.5, MeOH). UV/Vis (qualitative,
MeOH): 300, 320 (sh), 425 nm. CD (MeOH): λmax (∆ε) = 221 (3.9), 13C NMR (151 MHz, CDCl3): δ = 15.7, 16.2, 16.3 (each CH3), 22.1
288 (–0.4), 310 (1.1) nm. IR (KBr): ν = 3558 (m), 3389 (s, br), 2965 (CH3-20Ј), 24.3, 25.4, 27.4, 27.5 (each CH2), 29.3 (CH3-19Ј), 35.2
˜
(s), 2917 (ss), 2853 (s), 1694 (m), 1660 (ss), 1609 (s), 1471 (m), 1453
(CH2-12Ј), 38.9, 39.1 (C-4Ј and C-8Ј), 48.3 (CH-14Ј), 94.1 (C-15Ј),
(s), 1355 (m), 1325 (m), 1304 (m), 1255 (m), 1217 (m), 1159 (m), 120.5, 123.8 (each CHvin), 124.7 (C-2), 126.3 (CHvin), 133.99 (CH-
1108 (m), 1075 (m), 1036 (m), 986 (w), 962 (w), 910 (w), 849 (m), 6), 134.02, 135.7, 137.4 (each Cvin), 145.4 (C-5), 156.5 (C-3), 180.6
734 (w), 704 (w), 573 (w) cm–1. H NMR (600 MHz, [D6]acetone):
δ = 1.33 (s, 3 H, 19Ј-H), 1.48 (s, 3 H), 1.49 (s, 3 H, 20Ј-H), 1.55 (s,
6 H), 1.56 (s, 6 H), 1.60 (s, 3 H), 1.62 (s, 3 H), 1.80 (s, 3 H), 1.84–
2.22 (m, 24 H), 2.86 (dd, J = 13.3, 7.3 Hz, 1 H, 1Ј-HA), 2.98 (dd,
J = 10.2, 2.6 Hz, 1 H, 14Ј-H), 3.30 (dd, J = 13.3, 7.3 Hz, 1 H, 1Ј-
HB), 3.69 (dd, J = 15.5, 6.3 Hz, 1 H, 1ЈЈЈ-HA), 4.02 (dd, J = 15.5,
6.3 Hz, 1 H, 1ЈЈЈ-HB), 4.90–4.97 (m, 3 H), 5.07 (m, 2 H), 5.12 (t, J
= 6.4 Hz, 1 H), 5.22 (t, J = 5.3 Hz, 1 H, 2ЈЈЈ-H), 6.09 (s, 1 H, OH),
6.23 (s, 1 H, 2ЈЈ-H), 6.47 (br. s, 1 H, OH) ppm. 1H NMR
(600 MHz, CDCl3): δ = 1.42, 1.52, 1.57 (each s, 3 H), 1.58 (s, 6 H),
1.60 (s, 3 H), 1.61 (s, 3 H), 1.63 (s, 3 H), 1.68 (s, 3 H), 1.81–1.85
(m, 2 H), 1.87 (3 H), 1.90–2.17 (m, 22 H), 2.95 (dd, J = 13.1,
8.0 Hz, 1 H), 2.98 (dd, J = 10.0, 2.5 Hz, 1 H), 3.30 (dd, J = 13.1,
8.0 Hz, 1 H), 3.76 (dd, J = 16.2, 6.2 Hz, 1 H), 3.86 (dd, J = 16.2,
6.2 Hz, 1 H), 4.85–4.91 (m, 2 H), 4.95 (m, 1 H), 5.05–5.10 (m, 3
H), 5.35 (br. t, J = 6.2 Hz, 1 H), 6.35 (s, 1 H), 6.65 (br., 1 OH), 8.52
(br., 1 OH) ppm. 1H-coupled 13C NMR (151 MHz, [D6]acetone): δ
= 15.5 (CH3), 16.1 (CH3), 16.3 (CH3), 16.7 (CH3), 16.8 (CH3), 17.7
(CH3), 22.6 (Q, J = 126 Hz, CH3-20Ј), 25.3 (CH2), 25.8 (CH3-
19ЈЈЈ), 26.5 (CH2), 26.8 (CH2), 27.3 (CH2), 27.4 (CH2), 27.5 (Tm,
J = 120 Hz, CH2-1ЈЈЈ), 29.0 (Q, J = 117 Hz, CH3-19Ј), 30.8 (T, J
= 128 Hz, CH2-13Ј), 33.3 (T, J = 130 Hz, CH2-1Ј), 39.1 (CH2), 39.4
(CH2), 40.37 (2ϫCH2), 40.44 (CH2), 42.2 (T, J = 125.5 Hz, CH2-
4Ј), 51.0 (D, J = 135.5 Hz, C-14Ј), 68.2 (d, J = 6.1 Hz, C-5), 94.7
(br. m, C-15Ј), 97.1 (D, J = 161 Hz, C-2ЈЈ), 105.2 (d, J = 7.1 Hz,
(C-4), 185.6 (C-1) ppm. EI-MS: m/z (%) = 397 (21), 396 (83), 395
(31), 394 (100) [M+], 379 (30), 366 (8), 351 (8), 313 (30), 271 (17),
259 (15), 257 (14), 245 (80), 243 (38), 231 (40), 229 (28), 217 (22),
215 (25), 205 (20), 203 (20), 201 (18), 192 (54), 191 (62), 177 (45),
147 (14), 121 (19), 119 (15), 109 (13), 107 (16), 105 (17), 95 (15),
93 (21), 91 (27), 81 (36), 79 (24), 77 (19), 69 (21), 67 (28), 57 (20),
55 (35), 53 (18), 41 (47).
1
(+)-(1ЈЈS)-O-Camphanoyl-(14ЈR)-tridentoquinone (4): To a solution
of 1 (0.30 g, 0.73 mmol) and triethylamine (0.11 mL, 0.79 mmol) in
dry THF (15 mL) were added at 0 °C (1S)-(–)-camphanoyl chloride
(0.132 g, 0.61 mmol) and a few crystals of 4-(dimethylamino)pyr-
idine (DMAP). After stirring the mixture at room temp. overnight,
water (50 mL) was added and the product extracted with Et2O
(50 mL). The organic phase was washed with water and brine, dried
(MgSO4), and flash chromatographed on silica gel (hexanes/
EtOAc, 9:1) to yield ester 4 (196 mg, 54%) as an orange oil, which
crystallized from EtOH, m.p. 123–125 °C. Rf (TLC) = 0.22 (hex-
20
anes/EtOAc, 9:1). [α]D = +178.5 (c = 0.07, MeCN). IR (KBr): ν
˜
= 2972 (m), 2932 (m), 1799 (ss), 1678 (s), 1658 (s), 1609 (s), 1256
(m), 1167 (m), 1095 (m), 1042 (s) cm–1. 1H NMR (300 MHz,
CDCl3): δ = 1.16 (s, 6 H), 1.19 (s, 3 H), 1.37 (s, 3 H, 19Ј-H), 1.46
(s, 3 H, 18Ј-H), 1.53 (s, 3 H, 17Ј-H), 1.58 (s, 3 H, 20Ј-H), 1.71 (s,
3 H, 16Ј-H), 1.70–2.25 (m, 15 H, 6ϫCH2, 5ЈЈ-H2, 6ЈЈ-Hendo), 2.57
(ddd, J = 13.7, 10.8, 4.3 Hz, 1 H, 6ЈЈ-Hexo), 2.92 (dd, J = 13.7,
7.3 Hz, 1 H, 1Ј-HA), 3.06 (t, J = 4.8 Hz, 1 H, 14Ј-H), 3.27 (dd, J
= 13.7, 7.3 Hz, 1 H, 1Ј-HB), 4.86–4.96 (m, 2 H, 6Ј-H, 10Ј-H), 5.00
(br. t, J = 7 Hz, 1 H, 2Ј-H) ppm. 13C NMR (75 MHz, CDCl3): δ
= 9.9 (C-11ЈЈ), 16.0, 16.1, 16.5, 16.6, 16.7 (each CH3), 22.2, 22.9
(C-1Ј and C-20Ј), 24.2, 24.8, 27.1, 28.9, 31.2 (C-5Ј, C-9Ј, C-13Ј, C-
5ЈЈ, C-6ЈЈ), 29.6 (C-19Ј), 35.5 (C-12Ј), 38.96, 39.00 (C-4Ј and C-8Ј),
48.5 (CH-14Ј), 54.9, 55.2 (C-4ЈЈ and C-7ЈЈ), 90.9 (C-1ЈЈ), 94.9 (C-
15Ј), 118.6 (2ϫ, C-2, C-5), 122.4, 123.6, 126.2 (each CHvin), 133.2,
135.6, 137.9 (each Cvin), 149.1 (C-6), 157.1 (C-3), 164.8, 176.5 (C-
3ЈЈ and C-8ЈЈ), 177.9, 179.4 (C-1 and C-4) ppm. EI-MS (DI,
245 °C): m/z (%) = 593 (100) [M+ + 2H], 591 (27) [M+], 590 (64),
439 (11), 396 (14), 394 (20), 388 (16). 311 (12), 245 (16), 243 (16),
207 (15), 191 (16), 137 (11), 125 (16), 121 (17), 109 (28), 97 (17),
83 (72).
C-6), 116.9 (d, J = 5.1 Hz, C-6ЈЈ), 119.9 (Dm, J = 149 Hz, CHvin
-
2Ј), 124.8 (CHvin), 125.07 (CHvin), 125.10 (CHvin), 125.2 (CHvin),
125.5 (Dq, J = 148, 6 Hz, CHvin-2ЈЈЈ), 127.8 (CHvin), 128.71 (m, C-
2), 128.74 (m, C-5ЈЈ), 131.6 (“septet”, J = 6 Hz, Cvin-15ЈЈЈ), 134.0
(Cvin), 134.7 (m, Cvin-3ЈЈЈ), 135.4 (Cvin), 135.5 (Cvin), 136.2 (Cvin),
139.9 (m, C-4ЈЈ), 140.2 (m, Cvin-3Ј), 146.7 (br. s, C-3ЈЈ), 151.1 (d, J
= 4.0 Hz, C-1ЈЈ), 163.1 (d, J = 4 Hz, C-3), 188.2 (s, C-1), 191.6 (d,
J = 8.1 Hz, C-4) ppm. 1 CH3 signal obscured (in CDCl3 7 CH3
signals visible between δ = 15 and 18.5 ppm). C-C connectivities
observed in the 2D INADEQUATE experiment: C-1 ↔ C-2 ↔ C-
3 ↔ C-4 ↔ C-5 ↔ C-6 ↔ C-1; C-2 ↔ C-14Ј ↔ C-15Ј ↔ C-19Ј,
C-20Ј; C-13Ј ↔ C-14Ј; C-5 ↔ C-1Ј ↔ C-2Ј ↔ C-3Ј ↔ C-4Ј, C-
16Ј; C-5 ↔ C-6ЈЈ ↔ C-1ЈЈ ↔ C-2ЈЈ ↔ C-3ЈЈ ↔ C-4ЈЈ ↔ C-5ЈЈ ↔
C-6ЈЈ. EI-MS: m/z (%) = 807 (9) [M + 1]+, 806 (18) [M+], 805 (9),
804 (16),412 (21), 411 (28), 410 (93) [C26H34O4]+, 398 (26)
[C26H38O3]+, 396 (10), 395 (10), 329 (11), 261 (23), 259 (19), 247
(13), 245 (12), 243 (10), 220 (10), 209 (12), 208 (20), 207 (17), 206
(12), 194 (14), 193 (10), 179 (17), 177 (42), 147 (11), 140 (11), 139
(28), 138 (17), 137 (8), 135 (16), 123 (14), 121 (24), 109 (20), 107
(16), 95 (20), 93 (17), 81 (56), 79 (13), 69 (100). HR EI-MS: m/z =
806.5126 [M+] (calcd. for C52H70O7: 806.5122).
Tridentorubin Analogue 13: A solution of 1 (0.17 g, 0.41 mmol) and
12 in THF (2 mL) was stirred at room temp. for 12 h. After concen-
tration under reduced pressure, the product was purified by
chromatography on Sephadex LH-20 (acetone) to yield 13 (35 mg,
16%) as an orange oil. Rf (TLC) = 0.65 (solvent system A), orange-
brown spot. CD (MeOH): λmax (∆ε) = 215 (3.4), 287 (–0.6), 311
(1.0) nm. IR (KBr): ν = 2924 (s), 1698 (m), 1669 (ss), 1614 (s), 1446
˜
(s), 1372 (m), 1255 (w), 1152 (w), 1076 (w), 980 (w), 888 (w), 826
1
Deoxytridentoquinone (11):
5
lyophilized fruit bodies[12] were
(w) cm–1. H NMR (300 MHz, [D6]acetone): δ = 1.40, 1.52, 1.56,
worked up as described in the general procedure. The pale yellow
fractions from the HSCCC separation were treated with Et2O and
washed several times with water. Concentration of the dried
(MgSO4) organic phase yielded 11 (1.5 mg, 0.01% of dry-weight)
as a yellow oil. Rf (TLC) = 0.81 (solvent system A), yellow spot, +
NH3: no colour change. 1H NMR (600 MHz, CDCl3): δ = 1.35,
1.46 (each s, 3 H), 1.55 (s, 6 H), 1.64 (s, 3 H), 1.76–1.89 (m, 4 H),
1.59, 1.62 (each s, 3 H), 1.90–2.15 (m, 12 H), 2.84 (dd, J = 13.3,
7.3 Hz, 1 H, 1Ј-HA), 3.00–3.15 (m, 2 H, 1Ј-HB, 14Ј-H), 4.90–5.05
(m, 3 H, 2Ј-H, 6Ј-H, 10Ј-H), 6.75 (“s”, 1 H, 5ЈЈ-H), 6.98 (“s”, 2 H,
2ЈЈ-H, 3ЈЈ-H) ppm. 13C NMR (75 MHz, [D6]acetone): δ = 15.4,
16.1, 16.7 (each CH3), 22.6 (CH3-20Ј), 25.4 (CH2), 27.1 (CH2), 29.0
(CH3-19Ј), 31.0 (CH2-13Ј), 32.7 (CH2-1Ј), 39.1 (CH2), 39.4 (CH2),
42.0 (CH2-4Ј), 50.8 (CH-14Ј), 66.5 (C-5), 94.7 (C-15Ј), 106.3 (C-6),
1.94–2.18 (m, 8 H), 2.81 (dd, J = 15, 7.5 Hz, 1 H, 1Ј-HA), 3.02 (t, 108.4 (3ϫ, C-3ЈЈ, C-5ЈЈ, C-6ЈЈ),* 118.7 (CHvin-2Ј), 125.0 (CHvin),
822
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Eur. J. Org. Chem. 2008, 816–825