A. Comini et al. / Tetrahedron: Asymmetry 15 (2004) 617–625
625
5. Park, B. K.; Nakagawa, M.; Hirota, A.; Nakayama, M.
Agric. Biol. Chem. 1987, 51, 3443–3444.
with HLAP to a conversion of 35%. The same work up
was followed and methyl terebate with 76% ee was
25
D
6. (a) Maiti, G.; Roy, S. C. J. Chem. Soc., Perkin. Trans. 1
1996, 403–404; (b) Park, B. K.; Nakagawa, M.; Hirota, A.;
Nakayama, M. J. Antibiot. 1988, 41, 751–758.
7. Hoffmann, H. M. R.; Rabe, J. Angew. Chem., Int. Ed.
Engl. 1985, 24, 94–100, and references cited therein.
8. Tocanne, J.-F.; Asselineau, C. Bull. Soc. Chim. Fr. 1965,
3346–3348.
9. Crawforth, J. M.; Fawcett, J.; Rawlings, B. J. J. Chem.
Soc., Perkin Trans. 1 1998, 1721–1725.
10. Khokhlov, A. S.; Anisova, L. N.; Tovarova, I. I.; Kleiner,
E. M.; Kovalenko, I. V.; Krasilnikova, O. I.; Kornitskaya,
E. Ya.; Pliner, S. A. Z. Allgem. Mikrobiol. 1973, 13, 647–
655.
obtained. ½aꢀ ¼ )3.2 (c 1.70, CH3CN), De218 ¼ þ0:82
(CH3CN).
(S)-())-2,2-Dimethyl-5-oxo-tetrahydro-3-furancarboxylic
acid 6: 0.181 g of methyl terebate ())-15 with 76% ee was
hydrolysed in 13 mL of dioxane and 7 mL of 6 N HCl
under reflux for 1 h. After evaporation of the solvent, a
solution of aqueous NaHCO3 was added and extracted
with ether. The mother liquors were acidified with 6 N
HCl and extracted with diethyl ether. The organic phase
was dried over Na2SO4. The terebic acid obtained was
recrystallised from ethyl acetate (60% yield), 60% ee. Mp
25
D
11. Patrick, T. M., Jr.; Erikson, F. B. U.S. Patent 2,926,173,
1960 (C.A.N. 54:P11999d).
12. Tocanne, J.-F.; Asselineau, C. Bull. Soc. Chim. Fr. 1968,
2103–2105.
177–179 ꢂC (lit.24 198 ꢂC); ½aꢀ ¼ )7.3 (c 0.49, acetone)
25
[lit.24 ½aꢀ ¼ )13.7 (c 1.05, acetone)], De220 ¼ þ0:57
D
(CH3CN).
13. Mori, K. Tetrahedron 1983, 39, 3107–3109.
14. (a) Kurosawa, K.; Ollis, W. D.; Redman, B. T.; Suther-
land, I. O.; Gottlieb, O. R.; Alves, H. M. Chem. Commun.
Ethyl (S)-())-2,2-dimethyl-5-oxo-tetrahydro-3-furan-
carboxylate 16: ( )-16 was hydrolysed with HLAP to
high conversion values following the general procedure.
^
1968, 1265–1267; (b) Ito, S.; Fujise, Y.; Mori, A. Chem.
Commun. 1965, 595–596; (c) Uda, H.; Maruyama, M.;
Kabuki, K.; Fujise, S. Nippon Kagaku Zasshi 1964, 85,
279–285 (C.A.N. 61:14767f); (d) Fujise, S.; Maruyama,
M.; Uda, H. Nippon Kagaku Zasshi 1961, 82, 367–370
(C.A.N. 57:16428f).
Extraction with diethyl ether under basic conditions
25
D
gave ())-16 with 63% ee, ½aꢀ ¼ )4.3 (c 1.09, CH3CN),
De218 ¼ þ0:59 (CH3CN).
15. Gielen, M.; Dalil, H.; Willem, R.; Biesemans, M.; De Vos,
D. Eur. Pat. Appl. EP 848008; Chem. Abstr. 1998, 129,
67875.
Acknowledgements
16. Yamada, Y.; Sugamura, K.; Kondo, K.; Yanagimoto, M.;
Okada, H. J. Antibiot. 1987, 496–504.
17. Shono, T.; Hamaguchi, H.; Nishiguchi, I.; Sasaki, M.;
Miyamoto, T.; Miyamoto, M.; Fujita, S. Chem. Lett.
1981, 1217–1220.
Financial supports by the M.I.U.R., PRIN 2002 and the
University of Trieste are gratefully acknowledged.
References and notes
18. Chen, C.-S.; Fujimoto, Y.; Girdaukas, G.; Sih, C. J.
J. Am. Chem. Soc. 1982, 104, 7294–7299.
€
€
19. (a) Loughlin, W. A. Bioresour. Technol. 2000, 74, 49–62;
(b) Santaniello, E.; Ferraboschi, P.; Grisenti, P.; Manzoc-
chi, A. Chem. Rev. 1992, 92, 1071–1140; (c) Csuk, R.;
1. (a) Chhor, R. B.; Nosse, B.; Sorgel, S.; Bohm, C.; Seitz,
M.; Reiser, O. Chem. Eur. J. 2003, 9, 260–270; (b) Brecht-
Forster, A.; Fitremann, J.; Renaud, P. Helv. Chim. Acta
2002, 85, 3965–3974; (c) Loh, T.-P.; Lye, P.-L. Tetrahe-
dron Lett. 2001, 42, 3511–3514; (d) Kongsaeree, P.;
Meepowpan, P.; Thebtaranonth, Y. Tetrahedron: Asym-
metry 2001, 12, 1913–1922; (e) Bella, M.; Margarita, C.;
Orlando, C.; Orsini, M.; Parlanti, L.; Piancatelli, G.
Tetrahedron Lett. 2000, 41, 561–565; (f) Forzato, C.; Nitti,
P.; Pitacco, G.; Valentin, E. In Targets in Heterocyclic
Systems; Attanasi, O. A., Spinelli, D., Eds.; The Italian
Society of Chemistry, 1999, Vol. 3; p 93–115; (g) Vaupel,
A.; Knochel, P. J. Org. Chem. 1996, 61, 5743–5753; (h) de
Azevedo, B. M.; Murta, M. M.; Greene, A. E. J. Org.
Chem. 1992, 57, 4567–4569; (i) Mulzer, J.; Kattner, L.;
€
Glanzer, B. Chem. Rev. 1991, 91, 49–97; (d) Servi, S.
Synthesis 1990, 1–25.
20. (a) Forzato, C.; Nitti, P.; Pitacco, G.; Valentin, E.
Tetrahedron: Asymmetry 1999, 10, 1243–1254; (b) Naka-
mura, K.; Kawai, Y.; Ohno, A. Tetrahedron Lett. 1991, 32,
2927–2928.
21. Wermuth, C. G. J. Org. Chem. 1979, 44, 2406–2408.
22. Drioli, S.; Felluga, F.; Forzato, C.; Nitti, P.; Pitacco, G.;
Valentin, E. J. Mol. Catal. B: Enzymatic 1997, 3, 203–207.
23. Drioli, S.; Felluga, F.; Forzato, C.; Nitti, P.; Pitacco, G.
Chem. Commun. 1996, 1289–1290.
24. Hoffmann, N. Tetrahedron: Asymmetry 1994, 5, 879–886.
25. Ichihara, A.; Kawagishi, H.; Sasagawa, T.; Sakamura, S.
Agric. Biol. Chem. 1981, 45, 2163–2164.
26. (a) Beecham, A. F. Tetrahedron Lett. 1968, 3591–3594; (b)
Beecham, A. F. Tetrahedron Lett. 1968, 1, 2355–2360.
27. (a) Ishida, A.; Yamashita, S.; Takamuku, S. Bull. Chem.
Soc. Jpn. 1988, 61, 2229–2231; (b) Fukunishi, K.; Inoue,
Y.; Kishimoto, Y.; Mashio, F. J. Org. Chem. 1975, 40,
628–632.
€
Strecker, A. R.; Schroder, C.; Buschmann, J.; Lehmann,
C.; Luger, P. J. Am. Chem. Soc. 1991, 113, 4218–4229.
2. (a) Maier, M. S.; Marimon, D. I. G.; Stortz, C. A.; Adler,
M. T. J. Nat. Prod. 1999, 62, 1565–1567; (b) Drioli, S.;
Felluga, F.; Forzato, C.; Nitti, P.; Pitacco, G.; Valentin, E.
J. Org. Chem. 1998, 63, 2385–2388; (c) Mulzer, J.; Salimi,
N.; Hartl, H. Tetrahedron: Asymmetry 1993, 4, 457–471;
(d) Huneck, S.; Tonsberg, T.; Bohlmann, F. Phytochem-
istry 1986, 25, 453–459.
3. Mandal, P. K.; Roy, S. C. Tetrahedron 1999, 55, 11395–
11398.
4. Mahato, S. B.; Siddiqui, K. A. I.; Bhattacharya, G.;
Ghosal, T.; Miyahara, K.; Sholichin, M.; Kawasaki, T.
J. Nat. Prod. 1987, 50, 245–247.
28. Majeti, S. J. Org. Chem. 1972, 37, 2914–2916.
29. (a) Pohmakotr, M.; Reutrakul, V.; Phongpradit, T.;
Chansri, A. Chem. Lett. 1982, 687–690; (b) Fukunishi,
K.; Inoue, Y.; Kishimoto, Y.; Mashio, F. J. Org. Chem.
1975, 40, 628–632.
30. Brook, M. A.; Chan, T. H. Synthesis 1983, 3, 201–203.