H. Matsuda et al. / Tetrahedron 56 (2000) 7763±7777
7775
High-resolution positive-ion FAB-MS: Calcd for
C18H26NO4S (M1H)1: 352.1583. Found: 352.1571. IR
15-H2), [7.22 (1H, t, J8.0 Hz), 7.32 (2H, dd, J7.3,
8.0 Hz), 7.46 (2H, d, J7.3 Hz), arom.-H]. 13C NMR
(125 MHz, pyridine-d5) dc: given in Table 1. Positive-ion
FAB-MS: m/z 396 (M1H)1. Negative-ion FAB-MS: m/z
394 (M2H)2.
(KBr): 3420, 1782, 1655 cm21 1H NMR (500 MHz,
.
DMSO-d6) d: 1.34 (1H, dddd, J4.7, 5.2, 11.6, 17.1 Hz,
8-H), [1.77 (dddd, J3.7, 5.2, 8.9, 18.6 Hz), 1.90 (dddd,
J7.9, 9.4, 13.4, 18.6 Hz), 2-H2], 2.03 (1H, ddd, J5.2,
12.2, 17.2 Hz, 9-H), 2.17 (1H, dddd, J3.7, 4.6, 12.2,
17.1 Hz, 8-H), 2.32 (1H, dddd, J3.7, 9.5, 11.6, 14.6 Hz,
7-H), 2.39 (1H, ddd, J4.6, 4.7, 17.2 Hz, 9-H), 2.47 (2H, m,
3-H2), 2.73 (1H, ddd, J4.9, 8.3, 14.6 Hz, 11-H), 2.76 (1H,
dd, J8.3, 9.7 Hz, 5-H), [2.79 (1H, dd, J8.3, 13.8 Hz),
2.93 (1H, dd, J4.9, 13.8 Hz), 13-H2], [2.81 (1H, dd,
J5.2, 14.1 Hz), 3.03 (1H, dd, J3.7, 14.1 Hz), 30-H2],
2.90 (1H, ddd, J5.2, 8.3, 13.4 Hz, 1-H), 3.32 (1H, br dd,
20-H), 3.94 (1H, dd, J9.5, 9.7 Hz, 6-H), 4.73, 4.85 (1H
each, both s, 14-H2), 4.97, 5.03 (1H each, both br s, 15-
H2). 13C NMR (125 MHz, DMSO-d6) dc: given in Table
1. Positive-ion FAB-MS: m/z 352 (M1H)1. Negative-ion
FAB-MS: m/z 350 (M2H)2.
23: A white powder, [a]2D8113.78 (c0.1, MeOH). High-
resolution positive-ion FAB-MS: Calcd for C18H26NO5
(M1H)1: 336.1811. Found: 336.1804. IR (KBr): 3380,
1765, 1655 cm21 1H NMR (500 MHz, pyridine-d5) d:
.
1.24 (1H, m, 8-H), 1.74 (2H, m, 2-H2), 1.93 (1H, ddd,
J5.5, 12.2, 12.6 Hz, 9-H), 2.14 (1H, m, 8-H), 2.36 (1H,
m, 9-H), 2.40, 2.43 (1H each, both m, 3-H2), 2.44 (1H, m,
7-H), 2.57 (1H, ddd, J4.3, 5.8, 10.9 Hz, 11-H), 2.72 (1H,
br d, 1-H), 2.72 (1H, br d, 5-H), [3.18 (1H, dd, J4.3,
12.3 Hz), 3.41 (1H, dd, J5.8, 12.3 Hz), 13-H2], 3.90 (1H,
t, J4.9 Hz, 20-H), 3.95 (1H, dd, J8.2, 9.2 Hz, 6-H), 4.34
(2H, d, J4.9 Hz, 30-H2), 4.72, 4.82 (1H each, both br s,
14-H2), 5.06, 5.11 (1H each, both br s, 15-H2). 13C NMR
(125 MHz, pyridine-d5) dc: given in Table 1. Positive-ion
FAB-MS: m/z 336 (M1H)1. Negative-ion FAB-MS: m/z
334 (M2H)2.
20: A white powder, [a]D2726.48 (c0.2, MeOH). High-
resolution positive-ion FAB-MS: Calcd for C17H24NO4
(M1H)1: 306.1706. Found: 306.1710. IR (KBr): 3368,
1774, 1655 cm21
.
1H NMR (500 MHz, pyridine-d5) d:
24: A white powder, [a]2D7120.08 (c0.2, MeOH). High-
resolution positive-ion FAB-MS: Calcd for C20H30NO4S
(M1H)1: 380.1895. Found: 380.1890. IR (KBr): 3375,
1.29 (1H, m, 8-H), 1.76 (2H, m, 2-H2), 1.95 (1H, ddd,
J5.5, 12.5, 17.1 Hz, 9-H), 2.15, 2.39 (1H each, both m,
3-H2), 2.35 (1H, m, 9-H), 2.39 (1H, m, 8-H), 2.52 (1H, m,
7-H), 2.55 (1H, m, 11-H), 2.75 (1H, br d, 1-H), 2.75 (1H, br
d, 5-H), 3.18 (2H, br s, 13-H2), 3.73 (2H, s, 20-H2), 3.96 (1H,
dd, J8.8, 8.9 Hz, 6-H), 4.73, 4.83 (1H each, both s, 14-H2),
5.06, 5.33 (1H each, both s, 15-H2). 13C NMR (125 MHz,
pyridine-d5) dc: given in Table 1. Positive-ion FAB-MS:
m/z 306 (M1H)1.
1778, 1655 cm21 1H NMR (500 MHz, pyridine-d5) d:
.
1.28 (1H, m, 8-H), 1.76 (2H, m, 2-H2), 1.97 (1H, ddd,
J5.5, 12.2, 12.8 Hz, 9-H), 2.05 (3H, s, 50-H3), 2.15 (1H,
m, 8-H), 2.15, 2.31 (1H each, both m, 30-H2), 2.37 (1H, m,
9-H), 2.41 (1H, m, 7-H), 2.43 (2H, m, 3-H2), 2.58 (1H,
m, 11-H), 2.78 (1H, br dd, 1-H), 2.78 (1H, br dd, 5-H),
2.86 (2H, dd, J7.0, 7.9 Hz, 40-H2), [3.05 (1H, dd,
J7.3, 12.2 Hz), 3.35 (1H, dd, J6.1, 12.2 Hz), 13-
H2], 3.78 (1H, dd, J5.2, 8.0 Hz, 20-H), 3.96 (1H, dd,
J9.1, 9.8 Hz, 6-H), 4.85, 4.94 (1H each, both s, 14-
H2), 5.08, 5.18 (1H each, both br s, 15-H2). 13C NMR
(125 MHz, pyridine-d5) dc: given in Table 1. Positive-
ion FAB-MS: m/z 380 (M1H)1. Negative-ion FAB-MS:
m/z 378 (M2H)2.
21: A white powder, [a]2D6115.28 (c0.4, MeOH). High-
resolution positive-ion FAB-MS: Calcd for C21H32NO4
(M1H)1: 362.2331. Found: 362.2340. IR (KBr): 3370,
1778, 1655 cm21 1H NMR (500 MHz, pyridine-d5) d:
.
0.97, 0.97 (3H each, both d, J6.8 Hz, 50 and 60-H3), 1.27
(1H, m, 8-H), 1.69, 1.81 (1H each, both m, 30-H2), 1.77 (2H,
m, 2-H2), 1.96 (1H, m, 9-H), 2.07 (1H, m, 40-H), 2.14 (1H,
m, 8-H), 2.36 (1H, m, 9-H), 2.38, 2.45 (1H each, both m,
3-H2), 2.42 (1H, m, 7-H), 2.54 (1H, ddd, J4.9, 5.8,
11.3 Hz, 11-H), 2.78 (1H, m, 1-H), 2.78 (1H, m, 5-H),
[3.04 (1H, dd, J4.9, 12.2 Hz), 3.35 (1H, dd, J5.8,
12.2 Hz), 13-H2], 3.67 (1H, dd, J6.1, 8.5 Hz, 20-H),
4.74, 4.84 (1H each, both s, 14-H2), 5.07, 5.33 (1H each,
both br s, 15-H2). 13C NMR (125 MHz, pyridine-d5) dc:
given in Table 1. Positive-ion FAB-MS: m/z 362
(M1H)1. Negative-ion FAB-MS: m/z 360 (M2H)2.
Syntheses of saussureamines D (4) and E (5)
A solution of 7 (1160 mg, 5.0 mmol) in CHCl3 (5.0 ml) was
treated with m-CPBA (880 mg, 5.1 mmol) and the mixture
was stirred at 08C for 30 min. The reaction mixture was
poured into ice-water and the whole was extracted with
AcOEt. The AcOEt extract was successively washed with
saturated aqueous NaHCO3 and brine, then dried over
MgSO4 powder and ®ltered. Removal of the solvent from
the ®ltrate under reduced pressure furnished a residue,
which was puri®ed by silica gel column chromatography
(50 g, n-hexane±AcOEt2:1) to give costunolide-1,10-
epoxide (900 mg, 73%).
22: A white powder, [a]D2624.68 (c0.2, MeOH). High-
resolution positive-ion FAB-MS: Calcd for C24H30NO4
(M1H)1: 396.2175. Found: 396.2170. IR (KBr): 3328,
1774, 1655 cm21 1H NMR (500 MHz, pyridine-d5) d:
.
1.19 (1H, dddd, J4.8, 7.0, 12.8, 17.4 Hz, 8-H), 1.76 (2H,
m, 2-H2), 1.89 (1H, dd like, 9-H), 2.06 (1H, br dd, 8-H), 2.30
(1H, m, 7-H), 2.34 (1H, m, 9-H), 2.44 (2H, m, 3-H2), 2.47
(1H, m, 11-H), 2.70 (1H, br d, 5-H), 2.72 (1H, br d, 1-H),
[3.02 (1H, dd, J5.2, 12.2 Hz), 3.41 (1H, m), 13-H2],
[3.13(1H, dd, J7.9, 13.7 Hz), 3.42 (1H, m), 30-H2], 3.90
(1H, m, 20-H), 3.91 (1H, dd, J8.8, 9.5 Hz, 6-H), 4.72, 4.83
(1H each, both s, 14-H2), 5.06, 5.31 (1H each, both br s,
A solution of costunolide-1,10-epoxide (800 mg, 3.5 mmol)
in benzene (10.0 ml) was treated with BF3´Et2O (80 ml) and
the mixture was stirred at room temperature for 30 min. The
reaction mixture was poured into ice-water ant the whole
was extracted with AcOEt. The AcOEt extract was succes-
sively washed with 5% aqueous NaHCO3 and brine, then
dried over MgSO4 powder and ®ltered. Removal of the
solvent from the ®ltrate under reduced pressure furnished