1
038
H. Kiyota et al. / Tetrahedron: Asymmetry 12 (2001) 1035–1038
4.4. Enzymatic hydrolysis of (±)-6
Roche Diagnostics K. K. and Toyobo Co., Ltd. for the
gifts of various lipases.
A suspension of (±)-6 (220 mg, 0.820 mmol) and lipase
P (Amano, 200 mg) in hexane (2 mL) and 0.1 M
phosphate buffer (pH 7.0, 2 mL) was stirred vigorously
at 25°C for 5 days. The reaction was monitored by
TLC. The suspension was filtered through a Celite pad.
References
The filtrate was diluted with satd aq. NaHCO soln,
1. Recent reviews: (a) Wasternack, C.; Miersch, O.;
Kramell, R.; Hause, B.; Ward, J.; Beale, M.; Boland, W.;
Parthier, B.; Feussner, I. Fett/Lipid 1998, 100, 139–146;
(b) Beale, M. H.; Ward, J. L. Nat. Prod. Rep. 1998, 15,
533–548.
3
extracted with ether, washed with brine, dried over
MgSO4 and concentrated in vacuo. Purification by
silica gel column chromatography (hexane:EtOAc=5/
1
) afforded (+)-6 (130 mg, 0.484 mmol, 59.0%) and
(
(
(
−)-3 (74.0 mg, 0.327 mmol, 39.9%).
2. (a) Yoshioka, A.; Yamada, T. J. Synth. Org. Chem. Jpn.
1
990, 18, 56–64 (in Japanese); (b) Kataoka, H.; Yamada,
2
3
+)-6: [h] =+58.7 (c 1.09, CHCl ), e.e.=80.7%.
T.; Goto, K.; Tsuji, J. Tetrahedron 1987, 43, 4107–4112.
. Demole, E.; Lederer, E.; Mercier, D. Helv. Chim. Acta
1962, 45, 675–685.
D
3
3
4
2
3
−)-3: [h] =−67.7 (c 1.39, CHCl ), e.e.=91.4%.
D
3
. Koda, Y.; Kikuta, Y.; Kitahara, T.; Nishi, T.; Mori, K.
The e.e. values were calculated from the specific rota-
tion values of the compounds described in Section 4.3.
Phytochemistry 1992, 31, 1111–1114.
5. Montforts, F.-P.; Gesing-Zibulak, I.; Grammenos, W.
Helv. Chim. Acta 1989, 72, 1852–1859.
4
.5. (−)-Methyl jasmonate [natural] (−)-1
6. (a) Dart, R. K.; Kerry, S.; Marples, B. A. Enzy. Microb.
Technol. 1992, 14, 954–958; (b) Kerry, S.; Dart, R. K.;
Marples, B. A. Enzy. Microb. Technol. 1993, 15, 818–820;
(c) Yamane, H.; Takahashi, N.; Ueda, J.; Kato, J. Agric.
Biol. Chem. 1981, 45, 1709–1711; (d) Nishida, R.; Acree,
T. E.; Fukami, H. Agric. Biol. Chem. 1985, 49, 769–772;
(e) Okamoto, M.; Nakazawa, H. Biosci. Biotechnol.
Biochem. 1992, 56, 1172–1173.
A solution of (+)-3 (273 mg, 1.21 mmol), Dess–Martin
periodinane (667 mg, 1.58 mmol) in CH Cl (5 mL) was
stirred at 20°C for 1 h. The mixture was diluted with
EtOAc, quenched with satd aq. Na S O soln, washed
with satd aq. NaHCO soln, dried (MgSO ) and con-
centrated in vacuo. The residue was chromatographed
2
2
2
2
3
3
4
on silica gel (hexane/EtOAc=3:1) to afford (−)-1 (268
7. Recent reviews: (a) Mori, K. Synlett 1995, 1097–1109; (b)
Theil, F. Chem. Rev. 1995, 95, 2203–2227; (c) Schoffers,
E.; Golebiowski, A.; Johnson, C. R. Tetrahedron 1996,
2
2
mg, 1.19 mmol, 98%) as a colorless oil, [h] =−94.4 (c
D
5
23
D
1
.26, MeOH) {lit. [h] =−90.2 (c 1.03, MeOH)}.
52, 3769–3826; (d) Roberts, S. M.; Williamson, N. M.
4
.6. (+)-Methyl jasmonate (+)-1
Curr. Org. Chem. 1997, 1, 1–20; (e) Schmid, R. D.;
Verger, R. Angew. Chem., Int. Ed. Engl. 1998, 37, 1608–
1633.
In the same manner as described for (−)-1, (−)-3 (64.3
mg, 0.290 mmol) gave (+)-1 (43.4 mg, 0.193 mmol,
8. Dathe, W.; Schindler, C.; Schneider, G.; Schmidt, J.;
Porzel, A.; Jensen, E.; Yamaguchi, I. Phytochemistry
1991, 30, 1909–1914.
. (a) Seto, H.; Kamuro, Y.; Qian, Z.-h.; Shimizu, T. J.
Pesticide Sci. 1992, 17, 61–67; (b) Seto, H.; Nomura, E.;
Fujioka, S.; Koshino, H.; Suenaga, T.; Yoshida, S.
Biosci. Biotechnol. Biochem. 1999, 63, 361–367.
23
D D
5
20
6
7%), [h] =+86.3 (c 0.985, MeOH) {lit. [h] =+90.4
(
c 0.31, MeOH)}.
9
Acknowledgements
10. Takehara, J.; Oritani, T.; Yamashita, K. Agric. Biol.
We thank Nippon Zeon Co., Ltd. for the gift of
Chem. 1991, 55, 2939–2944.
11. Chen, C.-S.; Sih, C. J. Angew. Chem., Int. Ed. Engl. 1989,
28, 695–707.
®
(
±)-methyl jasmonate (Jasmoneige ). We also thank
Amano Pharmaceutical Co., Ltd., Nagase & Co., Ltd.,
.