7654
T. Kamo et al. / Tetrahedron 57 &2001) 7649±7656
617,000), 245 611,000), 274 66700), 308 63300), 319
63400), 340 62800); EIMS 6probe) 70 eV m/z 6%): 292
[M]1 6100), 275 [M2OH]1 637), 264 658), 247 663);
HREIMS m/z 6M1): calculated for C18H12O4, 292.0735;
found 292.0732; NMR dH 6acetone-d6, 300 MHz): 6.67
61H, s, 9-H), 6.99 62H, d, J8.7 Hz, 30,50-H), 7.05 61H, brs,
1-OH), 7.49 62H, d, J8.7 Hz, 20,60-H), 7.61 61H, d,
J8.5 Hz, 6-H), 7.76 61H, dd, J8.3, 7.2 Hz, 3-H), 8.12
61H, d, J8.5 Hz, 5-H), 8.33 61H, dd, J8.3, 1.1 Hz, 4-H),
8.4061H, dd, J7.2, 1.1 Hz, 2-H), 8.63 61H, brs, 40-OH).
30,50-H), 7.54 62H, d, J8.6 Hz, 20,60-H), 7.61 61H, d, J
8.5 Hz, 5-H), 147.67 61H, dd, J8.1, 7.1 Hz, 8-H), 8.05
61H, d, J8.5 Hz, 6-H), 8.13 61H, d, J7.1 Hz, 9-H), 8.26
61H, d, J8.1 Hz, 7-H), 8.55 61H, brs, 40-OH); NMR dC
6125 MHz, acetone-d6): 71.8 6C-3), 78.2 6C-2), 116.4
6C-30,50), 126.6 6C-9), 126.9 6C-8), 129.5 6C-6), 130.1
0
6C-9a), 131.06C-5), 131.4 6C-3a), 132.1 6C-2 ,60), 132.2
6C-9b), 132.5 6C-10), 134.06C-6a), 135.4 6C-7), 142.7
6C-4), 158.5 6C-40), 199.5 6C-1). See the literature4 for the
other spectral data; the assignment of signals in the 1H NMR
spectrum reported in the literature were partially in error.
Ethereal diazomethane was added to 11 65.0mg) dissolved
in 2 mL of MeOH, and the solution was left at room
temperature for 2 h. The solvent was evaporated, and the
residue was subjected to ODS column chromatography
617 g) using a mixture of MeOH±H2O 63:2) as the eluent.
The eluate was collected in fractions of 15 mL, and fractions
no. 9 and 10were evaporated to give 12 61.7 mg).
3.5.5. -2)-2,3-cis-2,3-Dihydro-2,3-dihydroxy-9--40-hydroxy-
25
phenyl)phenalen-1-one -8). [a]D 21068 6c 0.06,
MeOH); UV lmax 6MeOH) nm 61): 246 623,000), 287
69800), 320 66100); EIMS 6probe) 70 eV m/z 6%): 306
[M]1 66), 288 [M2H2O]1 659), 287 [M2H2O±H]1 6100),
271 620); HREIMS m/z 6M1): calculated for C19H14O4,
306.0892; found 306.0869; NMR dH 6500 MHz, acetone-
d6): 4.28 61H, d, J4.0Hz, 2-O H), 4.47 61H, d, J3.0Hz,
3-OH), 4.91 61H, dd, J4.0, 3.7 Hz, 2-H), 5.24 61H, dd,
J3.7, 3.0Hz, 3- H), 6.87 62H, d, J8.6 Hz, 30,50-H), 7.20
62H, d, J8.6 Hz, 20,60-H), 7.51 61H, d, J8.4 Hz, 8-H),
7.63 61H, dd, J8.2, 7.0Hz, 5- H), 7.74 61H, d, J7.0Hz,
4-H), 8.03 61H, d, J8.2 Hz, 6-H), 8.18 61H, d, J8.4 Hz,
7-H), 8.38 61H, s, 40-OH).
25
1
[a]D 1658 6c 0.17, CHCl3); the H NMR spectrum was
identical to that of natural 12.
3.5.9. -2S,3S)--1)-2,3-Dihydro-2,3-dihydroxy-4--40-meth-
25
oxyphenyl)phenalen-1-one -12). [a]D 1658 6c 0.70,
CHCl3); NMR dH 6500 MHz, CDCl3): 2.96 61H, s, 3-OH),
3.88 63H, s, 40-OCH3), 4.23 61H, s, 2-OH), 4.72 61H, d,
J3.1 Hz, 2-H), 5.3061H, d, J3.1 Hz, 3-H), 7.02 62H, d,
J8.7 Hz, 30,50-H), 7.57 61H, d, J8.6 Hz, 5-H), 7.6062H,
d, J8.7 Hz, 20,60-H), 7.63 61H, dd, J8.0, 7.1 Hz, 8-H),
7.96 61H, d, J8.6 Hz, 6-H), 8.15 61H, d, J8.0Hz, 7- H),
8.23 61H, d, J7.1 Hz, 9-H); NMR dC 6125 MHz, CDCl3):
55.4 6OCH3), 69.9 6C-3), 76.2 6C-2), 113.9 6C-30,50), 125.8
6C-8), 126.6 6C-9), 127.4 6C-6a), 127.9 6C-3a), 128.9 6C-6),
129.9 6C-5), 130.7 6C-20,60), 131.06C-9b), 132.06C-1 0),
132.7 6C-9a), 135.06C-7), 142.6 6C-4), 159.5 6C-4 0),
198.2 6C-1). See the literature4,9 for the other spectral
3.5.6. -1S,2R,3S)--2)-2,3-Dihydro-1,2,3-trihydroxy-4--40-
25
hydroxyphenyl)phenalene -9). [a]D 258 6c 0.49,
MeOH); UV lmax 6MeOH) nm 61): 231 624,000), 259
615,000), 290 66800); EIMS 6probe) 70 eV m/z 6%): 308
[M]1 646), 290[M 2H2O]1 653), 273 6100), 272 693);
HREIMS m/z 6M1): calculated for C19H16O4, 308.1048;
found 308.1041; NMR dH 6300 MHz, acetone-d6): 2.46
61H, s, 1-OH), 2.54 61H, d, 3-OH), 2.82 61H, d, 2-OH),
3.85 61H, dd, J9.7, 3.2 Hz, 2-H), 5.02 61H, d, J3.2 Hz,
3-H), 5.28 61H, d, J9.7 Hz, 1-H), 6.94 62H, d, J8.7 Hz,
30,50-H), 7.47 61H, d, J8.1 Hz, 5-H), 7.49 62H, d, J
8.7 Hz, 20,60-H), 7.58 61H, dd, J8.5, 7.6 Hz, 8-H), 7.84
61H, d, J8.1 Hz, 6-H), 7.84 61H, d, J7.6 Hz, 7-H), 7.90
61H, d, J8.5 Hz, 9-H); NMR dC 6125 MHz, acetone-d6):
70.0 6C-3), 70.5 6C-1), 76.1 6C-2), 116.1 6C-30,50), 124.3
6C-9), 126.8 6C-8), 127.8 6C-7), 129.3 6C-6), 129.5 6C-9b),
129.9 6C-5), 132.4 6C-20,60), 132.4 6C-3a), 133.4 6C-10), 133.7
6C-6a), 139.3 6C-9a), 141.4 6C-4), 158.1 6C-40). Ethereal
diazomethane was added to 9 64.9 mg) dissolved in 2 mL of
MeOH, and the solution was left at room temperature for 2 h.
The solvent was evaporated, and the residue was subjected to
ODS column chromatography 617 g) using a mixture of
MeOH±H2O 63:2) as the eluent. The eluate was collected in
fractions of 15 mL, and fractions no. 8±10were evaporated to
1
data; the assignment of signals in the H NMR spectrum
reported in the literature were partially in error. Compound
12 639 mg) in 12 mL of EtOH was stirred at room tempera-
ture for 2 h after addition of NaBH4 620mg). The solution
was acidi®ed to pH 3 with 1N HCl, and then extracted with
EtOAc 615 mL£3). The organic layer was washed with H2O
610mL £3), dried over Na2SO4, ®ltered and evaporated to
dryness. The residue was subjected to ODS column
chromatography 617 g) using a mixture of MeOH±H2O
63:2) as the eluent. The eluate was collected in fractions
of 15 mL, and fractions no. 9±12 and 14±17 were evapo-
rated to give 10 623.1 mg) and 1-epimer of 10 68.4 mg),
25
respectively. Compound 10. [a]D 2358 6c 2.31,
25
1
CHCl3); the H NMR spectrum was identical to that of
natural 10. 1-Epimer of 10. [a]D 21218 6c 0.84,
25
give 10 63.9 mg). [a]D 2348 6c 0.39, CHCl3); the 1H NMR
CHCl3); NMR dH 6500 MHz, CDCl3): 3.50±3.70 63H, brs,
1,2, and 3-OH), 4.08 61H, dd, J2.1, 2.1 Hz, 2-H), 5.05 61H,
d, J2.1 Hz, 1 or 3-H), 5.08 61H, d, J2.1 Hz, 1 or 3-H),
6.97 62H, d, J8.7 Hz, 30,50-H), 7.47 61H, d, J8.4 Hz,
5-H), 7.48 62H, d, J8.7 Hz, 20,60-H), 7.52 61H, dd, J
8.0, 6.7 Hz, 8-H), 7.6061H, d, J6.7 Hz, 7-H), 7.88 61H,
d, J8.0Hz, 9- H), 7.88 61H, d, J8.4 Hz, 6-H).
spectrum was identical to that of natural 10.
3.5.7.
-1S,2R,3S)--2)-2,3-Dihydro-1,2,3-trihydroxy-4-
-40-methoxyphenyl)phenalene -10). Mp 92±968C;
[a]D 2358 6c 0.31, CHCl3). See the literature7 for the
25
other spectral data.
3.5.8.
-2S,3S)--1)-2,3-Dihydro-2,3-dihydroxy-4--40-
3.5.10.
-2R,3S)--2)-2,3-Dihydro-2,3-dihydroxy-9--40-
25
25
hydroxyphenyl)phenalen-1-one -11). [a]D 1568 6c
1.15, MeOH); NMR dH 6500 MHz, acetone-d6): 4.5061H,
brs, 2-OH), 4.58 61H, brs, 3-OH), 4.79 61H, d, J3.1 Hz,
2-H), 5.28 61H, d, J3.1 Hz, 3-H), 6.98 62H, d, J8.6 Hz,
hydroxyphenyl)phenalen-1-one -13). [a]D 21378 6c
0.56, MeOH). See the literature10 for the other spectral
data. Compound 13 65.5 mg) in 2 mL of EtOH was stirred
at room temperature for 2 h after addition of NaBH4 62 mg).