Chemistry Letters Vol.32, No.9 (2003)
845
a)
b)
c)
d)
O
COOMe
OHC
COOMe
COOMe
COOMe
methy oleate (4)
OH
OH
5
(25.6% from 4)
7
6
OH
OH
O
e)
f)
+
1
COOMe
COOMe
COOMe
8
7.6%
49.4%
O-TBDMS
O-TBDMS
O
O-TBDMS
,4-heptadiyne (9)
8
(45.6% from 7)
10
11
O
g)
6.9%
h)
i)
(
±)-KODA (1)
COOMe
COOMe
7
82.1%
68.8%
O-TBDMS
OH
1
2
13
overall yield 2.35% from 4
j)
6
9R-KODA (1a)
overall yield 0.81% from 4
COOMe
3
3.6%
R1
R2
1
2
(
-)-6: R =H, R =OH
1
2
1
4: R =OAc, R =H
Scheme 1. Synthesis of (Æ)-KODA and 9R-KODA Reagents and conditions: a) O3/MeOH, then Me2S;b) vinylmagnesium bro-
mide/THF;c) MCPBA/CH 2Cl2-sat. aq NaHCO3;d) TBDMS-Cl/imidazole/DMF;e) BF 3-Et2O/n-BuLi/THF;f) H 2, Lindlar’s
cat. (10%)/toluene;g) Swern oxid.;h) 46% aq HF-CH 3CN;i) lipase PS/0.1 M phosphate buffer (pH7)-acetone (1:1);j) lipase
PS/vinyl acetate/pentane.
References and Notes
0.91(9H, s), 0.95(3H, t, J ¼ 7:5 Hz), 1.26–1.56(12H),
2.04(2H, m), 2.27(2H, t, J ¼ 7:5 Hz), 2.74(2H, t, J ¼
6:0 Hz), 3.34(2H, dd, J ¼ 5:0, 7.0 Hz), 3.64(3H, s),
4.03(1H, dd, J ¼ 5:5, 7.5 Hz), 5.28(1H, m), 5.38(1H, m),
5.56(2H, m).
1
M. Yokoyama, S. Yamaguchi, S. Inomata, K. Komatsu, S.
Yoshida, T. Iida, Y. Yokokawa, M. Yamaguchi, S. Kaihara,
and A. Takimoto, Plant Cell Physiol., 41, 110 (2000).
S. Yamaguchi, M. Yokoyama, T. Iida, M. Okai, O. Tanaka,
and A. Takimoto, Plant Cell Physiol., 42, 1201 (2001).
M. Suzuki, S. Yamaguchi, T. Iida, I. Hashimoto, H.
Teranishi, M. Mizoguchi, F. Yano, Y. Todoroki, N.
Watanabe, and M. Yokoyama, Plant Cell Physiol., 44, 35
2
3
9
1, colorless oil, C18H30O4, IR (film): 3420, 3020, 2936,
À1
1
2860, 1710, 1216, 766 cm
.
H NMR (CD3OD) ꢁ:
0.97(3H, t, J ¼ 7:5 Hz), 1.28–1.71(12H), 2.08(2H, m),
2.26(2H, t, J ¼ 7:5 Hz), 2.79(2H, m), 3.35(2H, t, J ¼
5:0 Hz), 4.10 (1H, m), 5.29 (1H, m), 5.40 (1H, m), 5.54
(2H, m).
(
2003).
T. Itoh, K. Sakabe, and K. Kudo, Tetrahedron Lett., 39,
071 (1998).
All new compounds were characterized by physicochemical
properties. The structures of the compounds (7, 8, 10, 11)
were supported by their spectral data, even though they
were diastereomeric mixtures.
4
5
4
10 Each reaction condition has not been optimized.
2
6
ꢁ
11 (À)-6, colorless oil, ½ꢀ
À3:41 (CHCl3), C12H22O3, IR
D
À1
1
(film): 3448, 3079, 2932, 2856, 1740, 1437, 1172 cm . H
NMR (CDCl3) ꢁ: 1.27–1.57 (12H), 2.26 (2H, t, J ¼ 7:5 Hz),
3.62 (3H, s), 4.04 (1H, m), 5.05 (1H, d, J ¼ 10:0 Hz), 5.17
(1H, dd, J ¼ 1:5, 10.0 Hz), 5.82 (1H, m).
6
7
Z.-B. Zhang, Z.-M. Wang, Y.-X. Wang, H.-Q. Liu, G.-X.
Lei, and M. Shi, Tetrahedron: Asymmetry, 10, 837 (1999).
1,4-Heptadiyne was prepared by a literature method: S.
Voerman and G. H. L. Rothschild, J. Chem. Ecol., 4, 531
12 I. Ohtani, T. Kusumi, Y. Kashman, and H. Kakisawa, J. Am.
Chem. Soc., 113, 4092 (1991).
2
6
ꢁ
13 1a, colorless oil, ½ꢀD À14:7 (MeOH), C18H30O4, IR and
1
(1978).
H NMR data were identical to those of 1.
26
þ13:1 ꢁ (CHCl3), C25H46O4Si, IR
8
12, colorless oil, ½ꢀ
14 S. Imamura and A. Takimoto, Bot. Mag., Tokyo, 68, 235
(1955).
15 The detailed activity will be presented elsewhere.
D
(
film): 3020, 2953, 2932, 2858, 1731, 1255, 1216,
1
À1
7
58 cm . H NMR (CDCl3) ꢁ: 0.03(3H, s), 0.04(3H, s),
Published on the web (Advance View) August 11, 2003;DOI 10.1246/cl.2003.844