May 2005
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1
(320), 0 (370); IR (CHCl3) cmꢃ1: 3607, 3442 (OH), 1661 (conj. CO); H-
Hax), 1.32 (3H, d, Jꢀ6.5 Hz, 9-Me), 1.60 (1H, ddd, Jꢀ13, 3.5, 2 Hz, 2-Heq),
1.60 (1H, dd, Jꢀ14, 9 Hz, 4-Hax), 2.03 (3H, s, OAc), 2.35 (1H, ddd, Jꢀ14, 5,
2 Hz, 4-Heq), 3.87 (1H, m, 3-H), 5.37 (1H, quint.d, Jꢀ6.5, 1 Hz, 9-H), 5.65
(1H, dd, Jꢀ15.5, 6.5 Hz, 8-H), 5.92 (1H, dd, Jꢀ15.5, 1 Hz, 7-H); CI-MS
m/z: 269.1754 [Calcd for C15H25O34 (MHꢄ) 269.1752].
NMR d (300 MHz, CDCl3): 1.00, 1.07 (each 3H, s, gem-Me), 1.30 (3H, d,
Jꢀ6.5 Hz, 9-Me), 1.91 (3H, s, 5-Me), 2.23, 2.45 (each 1H, d, Jꢀ17 Hz, 2-
H2), 4.41 (1H, quint.-like, Jꢀ6 Hz, 9-H), 5.77 (1H, d, Jꢀ15.5 Hz, 7-H), 5.87
(1H, dd, Jꢀ15.5, 5 Hz, 8-H), 5.90 (1H, br s, 4-H); CI-MS m/z: 225.1491
[Calcd for C13H21O3 (MHꢄ) 225.1490].
19b: A colorless oil. [a]D22 ꢃ65.3° (cꢀ1.21, MeOH); IR (CHCl3) cmꢃ1
:
(6S,9S)-Vomifoliol 3: A colorless oil. [a]D23 ꢄ197.8° (cꢀ0.80, MeOH);
CD (cꢀ0.0021, MeOH) De (l nm): ꢃ2.5 (205), 0 (209), ꢄ16.5 (241), 0
(287), ꢃ0.9 (320), 0 (370); CI-MS m/z: 225.1491 [Calcd for C13H21O3
(MHꢄ) 225.1490]. UV, IR and 1H-NMR spectra were identical with com-
pound 2.
1
3601, 3462 (OH), 1732 (OAc); H-NMR d (300 MHz, CDCl3): 0.98 (3H, s,
1-Me), 1.13, 1.14 (each 3H, s, 1-Me, 5-Me), 1.31 (3H, d, Jꢀ6.5 Hz, 9-Me),
1.33 (1H, ddd, Jꢀ12.5, 3.5, 1.5 Hz, 2-Heq), 1.57 (1H, dd, Jꢀ12.5, 11 Hz, 2-
Hax), 1.86 (1H, dd, Jꢀ15, 9 Hz, 4-Hax), 2.05 (3H, s, OAc), 2.18 (1H, ddd,
Jꢀ15, 7, 1.5 Hz, 4-Heq), 3.86 (1H, m, 3-H), 5.37 (1H, quint.d, Jꢀ6.5, 1 Hz,
9-H), 5.66 (1H, dd, Jꢀ15.5, 6.5 Hz, 8-H), 5.87 (1H, dd, Jꢀ15.5, 1 Hz, 7-H);
CI-MS m/z: 269.1743 [Calcd for C15H25O4 (MHꢄ) 269.1752].
(6R,9S)-Vomifoliol 4: Colorless needles (acetone–hexane). mp 108—
109 °C; [a]D24 ꢃ205.2° (cꢀ0.80, MeOH); CD (cꢀ0.0019, MeOH) De (l
nm): ꢄ2.6 (205), 0 (209), ꢃ16.5 (241), 0 (290), ꢄ0.9 (320), 0 (370); CI-MS
m/z: 225.1476 [Calcd for C13H21O3 (MHꢄ) 225.1490]. Anal. Calcd for
C13H20O3: C, 69.61; H, 8.99. Found: C, 69.75; H, 9.11. UV, IR and 1H-NMR
spectra were identical with compound 1.
b-Glucosidation of Alcohols 1—4 To a stirred suspension of tetra-O-
pivaloyl-a-D-glucosyl bromide 2420) (1.75 g, 3.13 mmol), (6S,9R)-alcohol 1
(350 mg, 1.46 mmol), N,N-tetramethylurea (0.67 ml, 5.6 mmol) and pow-
dered molecular sieves 4 Å (4.5 g) in dry CH2Cl2 (20 ml) was added AgOTf
(1.20 g, 4.7 mmol) at 0 °C. After being stirred at 0 °C for 20 min and r.t. for
1.5 h, the reaction was quenched with saturated aq. NaHCO3. The reaction
mixture was diluted with AcOEt and filtered through Celite. The organic
layer of the filtrate was washed with brine, dried and evaporated to give a
residue which was purified by CC (CH2Cl2–hexane–acetone, 4 : 4 : 1) to af-
ford the b-glucoside 22a (610 mg, 57%) as a colorless foam. The com-
pounds 23a (42%), 22b (83%) and 23b (85%) were prepared in the same
manner as described above.
Synthesis of Enones 20a, b and 21a, b Dess–Martin periodinane
(1.06 g, 2.50 mmol) was added to a stirred solution of the 3-hydroxy com-
pound 18a (517 mg, 1.93 mmol) in CH2Cl2 (20 ml) at r.t. Stirring was contin-
ued for an additional 1.5 h. After CH2Cl2 was evaporated off, the resulting
solids were washed with ether and filtered off. The filtrate was concentrated.
The residue was purified by SCC (acetone–hexane, 1 : 3) to afford the corre-
sponding ketone. This was dissolved in benzene (15 ml) and p-TsOH·H2O
(25 mg, 0.13 mmol) was added to it. After being stirred at r.t. for 17 h, the re-
action mixture was diluted with ether. The organic layer was washed succes-
sively with saturated aq. NaHCO3 and brine. Evaporation of the dried solu-
tion gave a residue, which was purified by SCC (acetone–hexane, 1 : 3) to
give the enone 20a (446 mg, 87% from 18a). The compounds 21a (90%),
20b (96%) and 21b (94%) were prepared in the same manner as described
above.
20a: Colorless needles (ether–hexane). mp 91—93 °C; [a]D23 ꢄ208.8°
(cꢀ1.07, MeOH); UV lmax(EtOH) nm: 236; IR (CHCl3) cmꢃ1: 3604, 3480
22a: [a]D24 ꢄ56.8° (cꢀ0.99, MeOH); UV lmax (EtOH) nm: 237; IR
(CHCl3) cmꢃ1: 3515 (OH), 1740 (COO), 1662 (conj. CO), 1624 (CꢀC); 1H-
NMR d (300 MHz, CDCl3): 1.03, 1.09 (each 3H, s, gem-Me), 1.11, 1.15,
1.16, 1.23 (each 9H, s, tert-Buꢂ4), 1.21 (3H, d, Jꢀ6.5 Hz, 9-Me), 1.88 (3H,
d, Jꢀ1 Hz, 5-Me), 2.24, 2.44 (each 1H, d, Jꢀ17 Hz, 2-H2), 3.65 (1H, ddd,
Jꢀ10, 4, 2 Hz, 5ꢁ-H), 3.94 (1H, dd, Jꢀ12.5, 4 Hz, 6ꢁ-H), 4.26 (1H, qd, Jꢀ
6.5, 5 Hz, 9-H), 4.38 (1H, dd, Jꢀ12.5, 2 Hz, 6ꢁ-H), 4.61 (1H, d, Jꢀ8 Hz, 1ꢁ-
H), 5.00 (1H, dd, Jꢀ9.5, 8 Hz, 2ꢁ-H), 5.14 (1H, t, Jꢀ9.5 Hz, 4ꢁ-H), 5.30
(1H, t, Jꢀ9.5 Hz, 3ꢁ-H), 5.74 (1H, d, Jꢀ15.5 Hz, 7-H), 5.80 (1H, dd, Jꢀ
15.5, 5 Hz, 8-H), 5.88 (1H, br s, 4-H); SI-MS m/z: 745.4141 [Calcd for
C39H62O12Na (Mꢄ+Na) 745.4136].
1
(OH), 1729 (OAc), 1661 (conj. CO), 1627 (CꢀC); H-NMR d (300 MHz,
CDCl3): 1.00, 1.08 (each 3H, s, gem-Me), 1.33 (3H, d, Jꢀ6.5 Hz, 9-Me),
1.89 (3H, d, Jꢀ1 Hz, 5-Me), 2.05 (3H, s, OAc), 2.25, 2.44 (each 1H, d, Jꢀ
17 Hz, 2-H2), 5.38 (1H, m, 9-H), 5.79 (2H, m, 7-H, 8-H), 5.92 (1H, quint.,
Jꢀ1 Hz, 4-H); EI-MS m/z: 266.1518 [Calcd for C15H22O4 (Mꢄ) 266.1517].
Anal. Calcd for C15H22O4: C, 67.64; H, 8.33. Found: C, 67.67; H, 8.31.
21a: Colorless needles (ether–hexane). mp 92—93 °C; [a]D23 ꢃ120.8° (cꢀ
1.01, MeOH); UV lmax(EtOH) nm: 236; IR (CHCl3) cmꢃ1: 3605, 3468
1
(OH), 1731 (OAc), 1662 (conj. CO), 1627 (CꢀC); H-NMR d (300 MHz,
CDCl3): 1.00, 1.08 (each 3H, s, gem-Me), 1.33 (3H, d, Jꢀ6.5 Hz, 9-Me),
1.89 (3H, d, Jꢀ1 Hz, 5-Me), 2.05 (3H, s, OAc), 2.25, 2.40 (each 1H, dd, Jꢀ
17 Hz, 2-H2), 5.38 (1H, m, 9-H), 5.78 (2H, m, 7-H, 8-H), 5.92 (1H, br s, Jꢀ
1 Hz, 4-H); EI-MS m/z: 266.1511 [Calcd for C15H22O4 (Mꢄ) 266.1517].
Anal. Calcd for C15H22O4: C, 67.64; H, 8.33. Found: C, 67.68; H, 8.25.
20b: Colorless needles (ether–hexane). mp 91—92 °C; [a]D23 ꢄ117.1° (cꢀ
0.98, MeOH); EI-MS m/z: 266.1529 [Calcd for C15H22O4 (Mꢄ) 266.1517].
Anal. Calcd for C15H22O4: C, 67.64; H, 8.33. Found: C, 67.50; H, 8.21. UV,
IR and 1H-NMR spectra were identical with compound 21a.
23a: [a]D28 ꢃ64.8° (cꢀ0.94, MeOH); UV lmax (EtOH) nm: 236; IR
(CHCl3) cmꢃ1: 3603, 3524 (OH), 1740 (COO), 1662 (conj. CO), 1626 (Cꢀ
1
C); H-NMR d (300 MHz, CDCl3): 0.98, 1.07 (each 3H, s, gem-Me), 1.11,
1.14, 1.15, 1.23 (each 9H, s, tert-Buꢂ4), 1.22 (3H, d, Jꢀ6.5 Hz, 9-Me), 1.90
(3H, d, Jꢀ1 Hz, 5-Me), 2.24, 2.42 (each 1H, d, Jꢀ17 Hz, 2-H2), 3.68 (1H,
ddd, Jꢀ10, 4.5, 2 Hz, 5ꢁ-H), 3.98 (1H, dd, Jꢀ12.5, 4.5 Hz, 6ꢁ-H), 4.31 (1H,
qd, Jꢀ6.5, 4.5 Hz, 9-H), 4.33 (1H, dd, Jꢀ12.5, 2 Hz, 6ꢁ-H), 4.62 (1H, d, Jꢀ
8 Hz, 1ꢁ-H), 5.01 (1H, dd, Jꢀ9.5, 8 Hz, 2ꢁ-H), 5.14 (1H, t, Jꢀ9.5 Hz, 4ꢁ-H),
5.31 (1H, t, Jꢀ9.5 Hz, 3ꢁ-H), 5.75 (1H, d, Jꢀ15.5 Hz, 7-H), 5.83 (1H, dd,
Jꢀ15.5, 4.5 Hz, 8-H), 5.89 (1H, br s, 4-H); SI-MS m/z: 745.4137 [Calcd for
C39H62O12Na (MꢄꢄNa) 745.4136].
21b: Colorless needles (ether–hexane). mp 91—92 °C; [a]D23 ꢃ221.6° (cꢀ
1.00, MeOH); EI-MS m/z: 266.1523 [Calcd for C15H22O4 (Mꢄ) 266.1517].
Anal. Calcd for C15H22O4: C, 67.64; H, 8.33. Found: C, 67.46; H, 8.25. UV,
IR and 1H-NMR spectra were identical with compound 20a.
Methanolysis of Compounds 20a, b and 21a, b A solution of NaOMe
(0.5 M in MeOH; 1.65 ml; 0.83 mmol) was added to a solution of the acetate
20a (440 mg, 1.65 mmol) in MeOH (15 ml) at r.t. and the mixture was stirred
at r.t. for 1.5 h. To this mixture was added Dowex 50W-X8 (Hꢄ) (1.2 g) and
stirring continued at r.t. for a further 15 min. After Dowex was filtered off,
the filtrate was evaporated to give a residue, which was purified by SCC
(acetone–hexane, 1 : 2) to give the alcohol 1 [(6S,9R)-vomifoliol] (315 mg,
85%). The compounds 2 (98%), 3 (96%) and 4 (94%) were prepared in the
same manner as described above.
22b: [a]D24 ꢄ63.3° (cꢀ0.77, MeOH); UV lmax (EtOH) nm: 236; IR
(CHCl3) cmꢃ1: 3604, 3528 (OH), 1740 (COO), 1664 (conj. CO), 1623 (Cꢀ
1
C); H-NMR d (300 MHz, CDCl3): 0.99, 1.08 (each 3H, s, gem-Me), 1.11,
1.15, 1.16, 1.21 (each 9H, s, tert-Buꢂ4), 1.29 (3H, d, Jꢀ6.5 Hz, 9-Me), 1.94
(3H, d, Jꢀ1 Hz, 5-Me), 2.28, 2.41 (each 1H, d, Jꢀ17 Hz, 2-H2), 3.61 (1H,
ddd, Jꢀ10, 6.5, 2 Hz, 5ꢁ-H), 4.02 (1H, dd, Jꢀ12, 6.5 Hz, 6ꢁ-H), 4.22 (1H,
dd, Jꢀ12, 2 Hz, 6ꢁ-H), 4.36 (1H, quint.-like, Jꢀ6.5 Hz, 9-H), 4.53 (1H, d,
Jꢀ8 Hz, 1ꢁ-H), 4.99 (1H, dd, Jꢀ9.5, 8 Hz, 2ꢁ-H), 5.09 (1H, t, Jꢀ9.5 Hz, 4ꢁ-
H), 5.26 (1H, t, Jꢀ9.5 Hz, 3ꢁ-H), 5.65 (1H, dd, Jꢀ16, 5.5 Hz, 8-H), 5.71
(1H, d, Jꢀ16 Hz, 7-H), 5.92 (1H, br s, 4-H); SI-MS m/z: 745.4128 [Calcd
for C39H62O12Na (Mꢄ+Na) 745.4136].
(6S,9R)-Vomifoliol 1: Colorless needles (acetone–hexane). mp 107—
109 °C; [a]D24 ꢄ214.1° (cꢀ0.64, MeOH); UV lmax (EtOH) nm: 237; CD (cꢀ
0.0021, MeOH) De (l nm): ꢃ2.5 (205), 0 (209), ꢄ16.3 (241), 0 (290), ꢃ0.9
23b: [a]D27 ꢃ53.1° (cꢀ1.04, MeOH); UV lmax (EtOH) nm: 235; IR
(CHCl3) cmꢃ1: 3605, 3514 (OH), 1740 (COO), 1665 (conj. CO), 1626 (Cꢀ
1
(320), 0 (370); IR (CHCl3) cmꢃ1: 3606, 3453 (OH), 1662 (conj. CO); H-
1
C); H-NMR d (300 MHz, CDCl3): 1.04, 1.10 (each 3H, s, gem-Me), 1.11,
NMR d (300 MHz, CDCl3): 1.02, 1.08 (each 3H, s, gem-Me), 1.29 (3H, d,
Jꢀ6.5 Hz, 9-Me), 1.90 (3H, s, 5-Me), 2.23, 2.44 (each 1H, d, Jꢀ17.5 Hz, 2-
H2), 4.40 (1H, qd, Jꢀ6.5, 5 Hz, 9-H), 5.78 (1H, d, Jꢀ16 Hz, 7-H), 5.85 (1H,
dd, Jꢀ16, 5 Hz, 8-H), 5.90 (1H, br s, 4-H); CI-MS m/z: 225.1494 [Calcd for
C13H21O3 (MHꢄ) 225.1490]. Anal. Calcd for C13H20O3: C, 69.61; H, 8.99.
Found: C, 69.54; H, 9.25.
1.14, 1.16, 1.22 (each 9H, s, tert-Buꢂ4), 1.27 (3H, d, Jꢀ6.5 Hz, 9-Me), 1.89
(3H, d, Jꢀ1 Hz, 5-Me), 2.26 (1H, dd, Jꢀ17, 0.5 Hz, 2-H), 2.40 (1H, d, Jꢀ
17 Hz, 2-H), 3.65 (1H, ddd, Jꢀ10, 6, 2 Hz, 5ꢁ-H), 4.04 (1H, dd, Jꢀ12.5,
6 Hz, 6ꢁ-H), 4.22 (1H, dd, Jꢀ12.5, 2 Hz, 6ꢁ-H), 4.37 (1H, quint.-like, Jꢀ
6.5 Hz, 9-H), 4.59 (1H, d, Jꢀ8 Hz, 1ꢁ-H), 4.98 (1H, dd, Jꢀ9.5, 8 Hz, 2ꢁ-H),
5.09 (1H, t, Jꢀ9.5 Hz, 4ꢁ-H), 5.28 (1H, t, Jꢀ9.5 Hz, 3ꢁ-H), 5.58 (1H, dd, Jꢀ
16, 7.5 Hz, 8-H), 5.72 (1H, d, Jꢀ16 Hz, 7-H), 5.91 (1H, br s, 4-H); SI-MS
m/z: 745.4136 [Calcd for C39H62O12Na (MꢄꢄNa) 745.4136].
(6R,9R)-Vomifoliol 2: A colorless oil. [a]D23 ꢃ195.8° (cꢀ0.95, MeOH);
UV lmax (MeOH) nm (e): 237 (11,500); UV lmax (EtOH) nm: 237; CD (cꢀ
0.0019, MeOH) De (l nm): ꢄ2.8 (205), 0 (209), ꢃ17.2 (242), 0 (290), ꢄ0.9