2
660
H. MAKABE et al
.
HREIMS: calcd. for C18
64.2471.
H
32O, 264.2453; found,
Me
29.49, 29.59, 29.66, 29.67, 29.69, 31.94, 33.44,
6.89, 118.31, 129.54, 138.92, 146.76, 172.03.
4
Si) d: 14.12, 19.21, 22.70, 28.80, 29.26, 29.37,
2
7
(
2R,3Z,5E)-4-Iodo-3,5-octadien-2-ol (
solution of compound 4 (132 mg, 0.5 mmol) in THF
3 ml), sodium bis(2-methoxyethoxy) aluminum
hydride (0.5 ml, 60 in toluene, 1.7 mmol) was
added at 0 C. The reaction mixture was stirred for
h, before a solution of iodine (460 mg, 1.8 mmol) in
THF (5 ml) was added dropwise. The reaction
mixture was stirred for 30 min at 0 C, allowed to
warm to 20 C, and quenched with a sat. Na
5
). To a
HREIMS: calcd. for C19
292.2390.
H
32
O , 292.2402; found,
2
(
2
5
z
(
+
)-Akolactone A (1b).
3
[
a
]
D
+
14.6 (c 0.36,
1
13
9
CHCl ). The H- and C-NMR, IR, and HRMS
spectra were identical with those of 1a.
5
9
Acknowledgments
9
2
S
2
O
3
solution. The mixture was extracted with ether. The
This work was supported in part by grant-aid from
the Japan Society for the Promotion of Science
(15780084). We thank Ms. Keiko Hashimoto of the
Faculty of Agriculture at Shinshu University for the
500 MHz NMR measurements.
organic solution was successively washed with sat.
NaHCO
trated. The crude product was puriˆed by ‰ash
chromatography (hexane AcOEt 1) to give 6
171 mg, 87 ) as a pale yellow oil. This product was
3
and brine, dried over MgSO , and concen-
4
W
=
5
W
(
z
used for the next step without further puriˆcation;
References
2
6
-
1
[
a
]
D
+
2.9 (
c
1.6, CHCl
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). IR (ˆlm)
n
max cm : 3346,
1
1
)
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925, 2853, 1637, 1465, 1060, 947. H-NMR (CDCl
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,
.
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Si)
d
: 0.88 (3H, t,
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.9 Hz), 5.83 (1H, d, 7.5 Hz), 6.04 (1H, dt,
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=
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J
=
2
)
2
0
1
2
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1
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-
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4
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)
)
)
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Et
3
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3 2
1
m
9
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(
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(
hexane
W
AcOEt
=
5
W
1) to give 1a (55 mg, 75
z
) as a
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2
2
pale yellow oil, [
a
]
D
-
14.9 (
c
0.55, CHCl
3
0.10, CHCl )t. IR
3
), natural
s
2
8
1)
akolactone A, [
a
]
D
=-13.2, (
c
-
1
(
ˆlm)
n
max cm : 3030, 2925, 2853, 1760, 1466, 1318,
084, 974. H-NMR (CDCl
1
1
J
6
6
7
3
, Me Si) d: 0.88 (3H, t,
4
7
)
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sis of the potent antitumor annonaceous acetogenin
=
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.09 (1H, d, 15.9 Hz), 6.79 (1H, dt, 15.9,
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=
J
=
(
(
+
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=
J
=
1
3
J
=
3
,