136
Vol. 55, No. 1
and concentrated in vacuo to yield a residue. Chromatography of the residue
on a silica gel (40 ml) column with n-hexane–EtOAc as the eluent yielded 1a
(5.0 mg, 95.0%) as a yellow oil.
(3H, s, H-12), 0.87 (9H, s, –CMe3), 0.05 (6H, s, –SiMe2).
Cucumegastigmane II (2): White powder, mp 96—97 °C, [a]D23 ꢀ62.89°
(cꢁ0.698, MeOH). UV lmax (MeOH) nm (log e): 235.5 (3.94). CD
Cucumegastigmane I Diacetate (1a): Yellow oil, [a]D29 ꢀ75.53° (cꢁ0.094, (cꢁ6.76ꢄ10ꢃ5 M, MeOH) De (nm): ꢀ11.09 (239.6), ꢃ0.60 (319.8). FAB-
CHCl3). UV lmax (CHCl3) nm (log e): 241.0 (3.74). FAB-MS m/z (pos.): 325
MS m/z (pos.): 403 [MꢀH]ꢀ, (neg.): 401 [MꢃH]ꢃ. HR-FAB-MS m/z (pos.):
[MꢀH]ꢀ, 265, 205, 121. HR-FAB-MS m/z: 325.1643 [MꢀH]ꢀ (Calcd for 403.1967 [MꢀH]ꢀ (Calcd for C19H31O9: 403.1968). NMR data: see Tables 1
C17H25O6: 325.1652). 1H-NMR (CDCl3, 400 MHz) d: 5.91 (1H, d-like, and 2.
Jꢁ1.2 Hz, H-4), 5.91 (1H, d, Jꢁ15.6 Hz, H-7), 5.77 (1H, dd, Jꢁ15.6,
6.5 Hz, H-8), 5.51 (1H, m, H-9), 4.23 (1H, dd, Jꢁ11.7, 4.0 Hz, H-10a), 4.13
(1H, dd, Jꢁ11.7, 6.6 Hz, H-10b), 2.44 (1H, d, Jꢁ17.1 Hz, H-2a), 2.27 (1H,
Enzymatic Hydrolysis of 216,17) A solution of 2 (7.4 mg) in acetate
buffer (pH 4.4, 2.0 ml) was treated with b-glucosidase (Oriental Yeast,
8.1 mg) and the solution was left standing at 38 °C for 20 h. The reaction so-
d, Jꢁ17.1 Hz, H-2b), 2.09 (3H, s, 10-OAc), 2.06 (3H, s, 9-OAc), 1.86 (3H, lution was poured into water (5 ml) and the whole was extracted with EtOAc
d, Jꢁ1.5 Hz, H-13), 1.08 (3H, s, H-11), 0.99 (3H, s, H-12). 13C-NMR
(CDCl3, 100 MHz) d: 197.3 (C-3), 170.4 (9-OCOCH3), 169.8 (10-
OCOCH3), 161.4 (C-5), 134.5 (C-7), 127.2 (C-4), 126.0 (C-8), 79.0 (C-6),
71.5 (C-9), 64.7 (C-10), 49.6 (C-2), 41.1 (C-1), 24.1 (C-12), 22.9 (C-11),
21.1 (10-OCOCH3), 20.8 (9-OCOCH3), 18.8 (C-13).
(5 mlꢄ5). The combined EtOAc extracts were dried with MgSO4, and con-
centrated in vacuo to yield 2a (2.2 mg, 49.7%) as a yellow oil. The water-
soluble part after neutralization using Amberlite (IRA-400, Organo) and
evaporation was shown to contain D-glucose, identified by TLC using a 2-
butanone–acetic acid–H2O (3 : 1 : 1) solvent system. Chromatography of the
water-soluble part on a silica gel (40 ml) column with EtOAc–MeOH as the
eluent yielded D-glucose (1.5 mg, 45.3%). D-Glucose: [a]D25 ꢀ28.58°
(cꢁ0.099, H2O, 24 h after being dissolved in H2O).
Treatment with TBDMSCl of 114) A solution of 1 (7.0 mg, 29.2 m mol)
in dry pyridine (0.2 ml) was stirred under an Ar atmosphere. Then, TBDM-
SCl (73.0 mmol, 1 M in dichloromethane) was added dropwise. The reaction
mixture was stirred for 6 h, after which time 5 ml of a saturated aqueous
Aglycone of Cucumegastigmane II (2a): Yellow oil, [a]D25 ꢀ144.53°
NH4Cl solution (5 ml) was added. The aqueous soluble part was extracted (cꢁ0.075, MeOH). UV lmax (MeOH) nm (log e): 236.5 (4.12). CD
with chloroform (5 mlꢄ3) and chloroform/n-BuOH (2 : 1, 5 mlꢄ3). The (cꢁ2.92ꢄ10ꢃ5 M, MeOH) De (nm): ꢀ12.39 (240.2), ꢃ0.76 (328.4). FAB-
combined extracts were dried with Na2SO4, and concentrated in vacuo to
yield a residue. Chromatography of the residue on a silica gel (40 ml) col-
umn with n-hexane–EtOAc as the eluent yielded 1b (6.6 mg, 63.9%) as a
yellow oil.
MS m/z (pos.): 241 [MꢀH]ꢀ, 207, 115. HR-FAB-MS m/z: 241.1453
1
[MꢀH]ꢀ (Calcd for C13H21O4: 241.1440). H-NMR (CD3OD, 400 MHz) d:
5.89 (1H, dd, Jꢁ15.7, 1.2 Hz, H-7), 5.88 (1H, s, H-4), 5.78 (1H, dd, Jꢁ15.7,
5.5 Hz, H-8), 4.19 (1H, m, H-9), 3.50 (1H, dd, Jꢁ11.0, 4.9 Hz, H-10a), 3.46
10-TBDMS-Cucumegastigmane I (1b): Yellow oil, [a]D27 ꢀ128.24° (1H, dd, Jꢁ11.0, 6.6 Hz, H-10b), 2.50 (1H, d, Jꢁ16.8 Hz, H-2a), 2.15 (1H,
(cꢁ0.170, CHCl3). UV lmax (CHCl3) nm (log e): 241.0 (4.02). FAB-MS m/z
d, Jꢁ16.8 Hz, H-2b), 1.92 (3H, d, Jꢁ1.2 Hz, H-13), 1.04 (3H, s, H-11), 1.02
(pos.): 355 [MꢀH]ꢀ, 337, 205, 121, 73. HR-FAB-MS m/z: 355.2312
(3H, s, H-12). 13C-NMR (CD3OD, 100 MHz) d: 200.7 (C-3), 166.9 (C-5),
[MꢀH]ꢀ (Calcd for C19H35O4Si: 355.2306). 1H-NMR (CDCl3, 400 MHz) d: 132.3 (C-7), 132.1 (C-8), 126.9 (C-4), 80.0 (C-6), 73.5 (C-9), 67.2 (C-10),
5.92 (1H, dd, Jꢁ15.6, 1.2 Hz, H-7), 5.91 (1H, d, Jꢁ1.5 Hz, H-4), 5.77 (1H,
dd, Jꢁ15.6, 5.1 Hz, H-8), 4.25 (1H, m, H-9), 3.66 (1H, dd, Jꢁ10.0, 3.9 Hz,
H-10a), 3.44 (1H, dd, Jꢁ10.0, 7.3 Hz, H-10b), 2.46 (1H, d, Jꢁ17.1 Hz, H-
2a), 2.24 (1H, dd, Jꢁ17.1, 1.0 Hz, H-2b), 1.89 (3H, d, Jꢁ1.5 Hz, H-13),
50.7 (C-2), 42.3 (C-1), 24.5 (C-12), 23.4 (C-11), 19.6 (C-13).
(ꢀ)-Dehydrovomifoliol (3): Yellow oil, [a]D28 ꢀ138.96° (cꢁ0.424,
MeOH). UV lmax (MeOH) nm (log e): 238.0 (4.19). CD (cꢁ3.15ꢄ10ꢃ5 M,
MeOH) De (nm): ꢀ27.00 (243.2). EI-MS m/z (rel. int. %): 222 (1) [M]ꢀ,
1.08 (3H, s, H-11), 1.02 (3H, s, H-12), 0.90 (9H, s, –CMe3), 0.08 (6H, s, 166 (25), 124 (100). HR-EI-MS m/z: 222.1251 [M]ꢀ (Calcd for C13H18O3:
–SiMe2). 13C-NMR (CDCl3, 100 MHz) d: 197.4 (C-3), 162.0 (C-5), 131.2 222.1256). NMR data: see Tables 1 and 2.
(C-7), 129.9 (C-8), 126.7 (C-4), 79.1 (C-6), 71.8 (C-9), 66.8 (C-10), 49.6
(C-2), 41.0 (C-1), 25.8 (–CMe3), 24.0 (C-12), 22.8 (C-11), 18.8 (C-13), 18.2
(–CMe3), ꢃ5.3, ꢃ5.4 (–SiMe2).
References
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2) Enslin P. R., Hugo J. M., Norton K. B., Rivett D. E. A., J. Chem. Soc.,
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Preparation of the (R)- and (S)-MTPA Derivatives 1c and 1d from
1b15) (R)-MTPA working solution ((R)-MTPA 27.8 mg and DCC 29.1 mg
in 0.5 ml of dry dichloromethane) was prepared. Compound 1b (2.8 mg,
7.9 mmol) and DMAP (0.9 mg) were dissolved in dry dichloromethane
(0.5 ml) and stirred at room temperature for 30 min. Then, (R)-MTPA work-
ing solution was added and stirred at room temperature for 1 h. After the ad-
dition of 5 ml each of water and dichloromethane, the solution was washed
successively with 5% HCl (5 ml), saturated NaHCO3 (5 ml) and brine (5 ml).
The organic soluble part was dried with Na2SO4, and concentrated in vacuo
to yield a residue. Chromatography of the residue on a silica gel (40 ml) col-
umn using n-hexane–EtOAc as the eluent yielded 1c (2.7 mg, 60.0%) as a
colorless oil. Using a similar procedure, 1d (4.6 mg, 86.6%) was prepared
from 1b (3.3 mg, 9.3 mmol) with (S)-MTPA (33.1 mg), DCC (25.9 mg) and
DMAP (1.3 mg).
10-TBDMS-Cucumegastigmane I 9-O-(R)-MTPA Ester (1c): Colorless
oil, [a]D29 ꢀ42.73° (cꢁ0.044, CHCl3). UV lmax (CHCl3) nm (log e): 241.0
(3.68). FAB-MS m/z (pos.): 571 [MꢀH]ꢀ, 337, 205, 189, 121, 73. HR-FAB- 10) Luedemann H. D., Nimz H., Makromol. Chem., 175, 2393—2407
1
MS m/z: 571.2706 [MꢀH]ꢀ (Calcd for C29H42O6F3Si: 571.2704). H-NMR
(CDCl3, 400 MHz) d: 7.52—7.34 (5H, m, –Ph), 5.96 (1H, d, Jꢁ15.4 Hz, H-
7), 5.89 (1H, s, H-4), 5.85 (1H, dd, Jꢁ15.4, 7.0 Hz, H-8), 5.53 (1H, m, H-9),
3.75 (1H, dd, Jꢁ10.9, 6.1 Hz, H-10a), 3.69 (1H, dd, Jꢁ10.9, 4.8 Hz, H-10b),
3.50 (3H, d, Jꢁ1.0 Hz, –OMe), 2.39 (1H, d, Jꢁ17.0 Hz, H-2a), 2.24 (1H, d,
(1974).
11) Nakajima E., Nakano H., Yamada K., Shigemori H., Hasegawa K.,
Phytochemistry, 61, 863—865 (2002).
12) Li G., Deng Z., Li J., Fu H., Lin W., J. Chin. Pharm. Sci., 13, 81—86
(2004).
Jꢁ17.0 Hz, H-2b), 1.85 (3H, d, Jꢁ1.2 Hz, H-13), 1.06 (3H, s, H-11), 0.94 13) Stueber D., Grant D. M., J. Am. Chem. Soc., 124, 10539—10551
(3H, s, H-12), 0.84 (9H, s, –CMe3), 0.01 (6H, s, –SiMe2).
(2002).
10-TBDMS-Cucumegastigmane I 9-O-(S)-MTPA Ester (1d): Colorless
14) Moreno-Dorado F. J., Guerra F. M., Ortega M. J., Zubia E., Massanet
G. M., Tetrahedron: Asymmetry, 14, 503—510 (2003).
oil, [a]D28 ꢀ70.94° (cꢁ0.064, CHCl3). UV lmax (CHCl3) nm (log e): 241.0
(4.12). FAB-MS m/z (pos.): 571 [MꢀH]ꢀ, 337, 205, 189, 121, 73. HR-FAB- 15) Otsuka H., Kijima H., Hirata E., Shinzato T., Takushi A., Bando M.,
1
MS m/z: 571.2706 [MꢀH]ꢀ (Calcd for C29H42O6F3Si: 571.2704). H-NMR
Takeda Y., Chem. Pharm. Bull., 51, 286—290 (2003).
(CDCl3, 400 MHz) d: 7.54—7.32 (5H, m, –Ph), 5.87 (1H, s, H-4), 5.79 (1H, 16) Murakami T., Kishi A., Matsuda H., Hattori M., Yoshikawa M., Chem.
d, Jꢁ15.6 Hz, H-7), 5.74 (1H, d, Jꢁ15.6 Hz, H-8), 5.59 (1H, m, H-9), 3.76 Pharm. Bull., 49, 845—848 (2001).
(1H, dd, Jꢁ9.8, 5.4 Hz, H-10a), 3.72 (1H, dd, Jꢁ9.8, 3.4 Hz, H-10b), 3.58 17) Yu Q., Matsunami K., Otsuka H., Takeda Y., Chem. Pharm. Bull., 53,
(3H, d, Jꢁ1.0 Hz, –OMe), 2.28 (1H, d, Jꢁ17.0 Hz, H-2a), 2.19 (1H, d,
Jꢁ17.0 Hz, H-2b), 1.82 (3H, d, Jꢁ1.5 Hz, H-13), 1.04 (3H, s, H-11), 0.91
800—807 (2005).