A Novel Synthetic Method of the (±)-(3aα,8aα)-Ethyl 8β-Hydroxy-6β-methyl-2-oxooctahydro-2H-cyclohepta[b]furan-3α- carboxylate and Its Chemical Transformation to (±)-(3aα,8aα) -3α,6β-Dimethyl-3,3a,4,5,6,8a-hexahydro-2H-Cyclohepta[b]furan-2-one, (+)- and (-)-7β-(2-Acetoxy-1α-methylethyl)-4β-methyl-2- cyclohepten-1β

Journal of Organic Chemistry

Volumn 63, Issue 4, 1998, Pages 920-929

  Shimoma, Fumito ^a   Kusaka, Haruhiko ^a   Wada, Katsuaki ^a   Azami, Hidenori ^a   Yasunami, Masafumi ^a   Suzuki, Toshio ^a   Hagiwara, Hisahiro ^a   Ando, Masayoshi ^b  

^a NIIGATA UNIVERSITY   (Japan)

^b TOHOKU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

4,5 SECOGUAIANOLIDE; 4,5 SECOPSEUDOGUAIANOLIDE; GUAIANOLIDE DERIVATIVE; OCTALACTIN; PSEUDOGUAIANOLIDE DERIVATIVE; UNCLASSIFIED DRUG;

ACETYLATION; ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; ENANTIOMER; HYDROGENATION; NUCLEAR OVERHAUSER EFFECT; OXIDATION; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; SYNTHESIS;

EID: 0032548979     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo971529q     Document Type: Article

References (53)

1. Connolly, J. D.; Hill, R. A. Dictionary of Terpenoids, Vol. 1; Chapman and Hall: London, 1991; pp 463-545.
2. Rodriguez, E.; Tower, G. H. N.; Mitchell, J. C. Phytochemistry 1976, 15, 1573.
3. Ando, M. J. Synth. Org. Chem. 1992, 50, 858.
4. Cordell, G. A.; Farnsworth, N. R. J. Nat. Prod. 1977, 40, 1.
5. Kupchan, S. M.; Eakin, M. A.; Thomas, A. M. J. Med. Chem. 1971, 14, 1147.
6. Lee, K.-H.; Huang, E.-S.; Piantadosi, C.; Pagano, J. S.; Geissman, T. A. Cancer Res. 1971, 31, 1649.
7. Kupchan, S. M.; Kelsey, J. E.; Maruyama, M.; Cassady, J. M. Tetrahedron Lett. 1968, 3517.
8. Jolad, S. D.; Wiedhopf, R. M.; Cole, J. D. J. Pharm. Sci. 1974, 63, 1321.
9. Ogura, M.; Cordell, G. A.; Farnsworth, N. R. Phytochemistry 1978, 17, 957.
10. Cassady, J. M.; Suttness, M. Anticancer Agent Based on Natural Product Models; Cassady, J. M., Douros, J., Eds.; Academic Press: New York; 1980; pp 206-224.
11. Ando, M.; Kusaka, H.; Ohara, H.; Takase, K.; Yamaoka, H.; Yanagi, Y. J. Org. Chem. 1989, 54, 1952.
12. Ando, M.; Isogai, K.; Azami, H.; Hirata, N.; Yanagi, Y. J. Nat. Prod. 1991, 54, 1017.
13. Ando, M.; Isogai, K.; Azami, H.; Hirata, N.; Yamazaki, H.; Yanagi, Y. J. Nat. Prod. 1992, 55, 1620.
14. Ando, M.; Wada, T.; Kusaka, H.; Takase, K.; Hirata, N.; Yanagi, Y. J. Org. Chem. 1987, 52, 4792.
15. Robles, M.; Aregullin, M.; West, J.; Rodriguez, E. Planta Med. 1995, 67, 199.
16. Vichnewski, W.; Gilbert, B. Phytochemistry 1972, 11, 2563.
17. Garcia, M.; Da Silva, A. J. R.; Baker, P. M.; Gilbert, B.; Rabi, J. A. Phytochemistry 1976, 15, 331.
18. Sánchez-Viesca, F.; Ramo, J. Tetrahedron 1963, 19, 1285.
19. Bates, R. B.; Cekan, Z.; Procházka, V.; Herout, V. Tetrahedron
20. Jöchel, W. Angew. Chem., Int. Ed. Engt. 1962, 1, 541.
21. Taniguchi, M.; Kataoka, T.; Suzuki, H.; Uramoto, M.; Ando, M.; Arao, K.; Magae, J.; Nishimura, T.; Otake, N.; Nagai, K. Biosci. Biotech. Biochem. 1995, 59, 2064.
22. Osawa, T.; Suzuki, A.; Tamura, S. Agric. Biol. Chem. 1971, 35, 1966.
23. Osawa, T.; Taylar, D.; Suzuki, A.; Tamura, S. Tetrahedron Lett. 1977, 1169.
24. Asakawa, Y.; Takemoto, T. Phytochemistry 1979, 18, 285.
25. Asakawa, Y.; Matsuda, R.; Takemoto, T. Phytochemistry 1980, 19, 567.
26. Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Plavac, F.; White, C. T. The Total Synthesis of Natural products, Vol, 5; ApSimons, J., Ed.; Wiley: New York, 1982, and references cited therein.
27. The pseudoguaianolides which possess the β-oriented secondary methyl group at C-10 and the cis-fused γ-lactone moiety at the C-6, 7 position are called arnbrosanolides. The references of the total syntheses of ambrosanolides are shown below: (a) Marshall, J. A.; Snyder, W. R. J. Org. Chem. 1975, 40, 1656. This paper did not report the total synthesis of ambrosanolides but described important synthetic methodology of ambrosanolides. (b) Kretchmer, R. A.; Thompson, W. J. J. Am. Chem. Soc. 1976, 98, 3379. (c) DeClercq, P.; Vandewalle, M. J. Org. Chem. 1977, 42, 3447. (d) Kok, P.; DeClercq, P.; Vandewalle, M. Bull. Soc. Chem. Belg. 1978, 87, 615. (e) Grieco, P. A.; Ohfune, Y.; Majetich, G. J. Am. Chem. Soc. 1977, 99, 7393. (f) Grieco, P. A.; Oguri, T.; Burke, S.; Rodriguez, E.; DeTitta, G. T.; Fortier, S. J. Org. Chem. 1978, 43, 4552. (g) Roberts, M. R.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7626. Quallich, G. J.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7627. (h) Demuynck, M.; DeClercq, P.; Vandewalle, M. J. Org. Chem. 1979, 44, 4863. Heathcock, C. H.; Tice, C. M.; Germorth, T. C. J. Am. Chem. Soc. 1982, 104, 6081.
28. The pseudoguaianolides which possess the β-oriented secondary methyl group at C-10 and the cis-fused γ-lactone moiety at the C-6, 7 position are called arnbrosanolides. The references of the total syntheses of ambrosanolides are shown below: (a) Marshall, J. A.; Snyder, W. R. J. Org. Chem. 1975, 40, 1656. This paper did not report the total synthesis of ambrosanolides but described important synthetic methodology of ambrosanolides. (b) Kretchmer, R. A.; Thompson, W. J. J. Am. Chem. Soc. 1976, 98, 3379. (c) DeClercq, P.; Vandewalle, M. J. Org. Chem. 1977, 42, 3447. (d) Kok, P.; DeClercq, P.; Vandewalle, M. Bull. Soc. Chem. Belg. 1978, 87, 615. (e) Grieco, P. A.; Ohfune, Y.; Majetich, G. J. Am. Chem. Soc. 1977, 99, 7393. (f) Grieco, P. A.; Oguri, T.; Burke, S.; Rodriguez, E.; DeTitta, G. T.; Fortier, S. J. Org. Chem. 1978, 43, 4552. (g) Roberts, M. R.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7626. Quallich, G. J.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7627. (h) Demuynck, M.; DeClercq, P.; Vandewalle, M. J. Org. Chem. 1979, 44, 4863. Heathcock, C. H.; Tice, C. M.; Germorth, T. C. J. Am. Chem. Soc. 1982, 104, 6081.
29. The pseudoguaianolides which possess the β-oriented secondary methyl group at C-10 and the cis-fused γ-lactone moiety at the C-6, 7 position are called arnbrosanolides. The references of the total syntheses of ambrosanolides are shown below: (a) Marshall, J. A.; Snyder, W. R. J. Org. Chem. 1975, 40, 1656. This paper did not report the total synthesis of ambrosanolides but described important synthetic methodology of ambrosanolides. (b) Kretchmer, R. A.; Thompson, W. J. J. Am. Chem. Soc. 1976, 98, 3379. (c) DeClercq, P.; Vandewalle, M. J. Org. Chem. 1977, 42, 3447. (d) Kok, P.; DeClercq, P.; Vandewalle, M. Bull. Soc. Chem. Belg. 1978, 87, 615. (e) Grieco, P. A.; Ohfune, Y.; Majetich, G. J. Am. Chem. Soc. 1977, 99, 7393. (f) Grieco, P. A.; Oguri, T.; Burke, S.; Rodriguez, E.; DeTitta, G. T.; Fortier, S. J. Org. Chem. 1978, 43, 4552. (g) Roberts, M. R.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7626. Quallich, G. J.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7627. (h) Demuynck, M.; DeClercq, P.; Vandewalle, M. J. Org. Chem. 1979, 44, 4863. Heathcock, C. H.; Tice, C. M.; Germorth, T. C. J. Am. Chem. Soc. 1982, 104, 6081.
30. The pseudoguaianolides which possess the β-oriented secondary methyl group at C-10 and the cis-fused γ-lactone moiety at the C-6, 7 position are called arnbrosanolides. The references of the total syntheses of ambrosanolides are shown below: (a) Marshall, J. A.; Snyder, W. R. J. Org. Chem. 1975, 40, 1656. This paper did not report the total synthesis of ambrosanolides but described important synthetic methodology of ambrosanolides. (b) Kretchmer, R. A.; Thompson, W. J. J. Am. Chem. Soc. 1976, 98, 3379. (c) DeClercq, P.; Vandewalle, M. J. Org. Chem. 1977, 42, 3447. (d) Kok, P.; DeClercq, P.; Vandewalle, M. Bull. Soc. Chem. Belg. 1978, 87, 615. (e) Grieco, P. A.; Ohfune, Y.; Majetich, G. J. Am. Chem. Soc. 1977, 99, 7393. (f) Grieco, P. A.; Oguri, T.; Burke, S.; Rodriguez, E.; DeTitta, G. T.; Fortier, S. J. Org. Chem. 1978, 43, 4552. (g) Roberts, M. R.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7626. Quallich, G. J.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7627. (h) Demuynck, M.; DeClercq, P.; Vandewalle, M. J. Org. Chem. 1979, 44, 4863. Heathcock, C. H.; Tice, C. M.; Germorth, T. C. J. Am. Chem. Soc. 1982, 104, 6081.
31. The pseudoguaianolides which possess the β-oriented secondary methyl group at C-10 and the cis-fused γ-lactone moiety at the C-6, 7 position are called arnbrosanolides. The references of the total syntheses of ambrosanolides are shown below: (a) Marshall, J. A.; Snyder, W. R. J. Org. Chem. 1975, 40, 1656. This paper did not report the total synthesis of ambrosanolides but described important synthetic methodology of ambrosanolides. (b) Kretchmer, R. A.; Thompson, W. J. J. Am. Chem. Soc. 1976, 98, 3379. (c) DeClercq, P.; Vandewalle, M. J. Org. Chem. 1977, 42, 3447. (d) Kok, P.; DeClercq, P.; Vandewalle, M. Bull. Soc. Chem. Belg. 1978, 87, 615. (e) Grieco, P. A.; Ohfune, Y.; Majetich, G. J. Am. Chem. Soc. 1977, 99, 7393. (f) Grieco, P. A.; Oguri, T.; Burke, S.; Rodriguez, E.; DeTitta, G. T.; Fortier, S. J. Org. Chem. 1978, 43, 4552. (g) Roberts, M. R.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7626. Quallich, G. J.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7627. (h) Demuynck, M.; DeClercq, P.; Vandewalle, M. J. Org. Chem. 1979, 44, 4863. Heathcock, C. H.; Tice, C. M.; Germorth, T. C. J. Am. Chem. Soc. 1982, 104, 6081.
32. The pseudoguaianolides which possess the β-oriented secondary methyl group at C-10 and the cis-fused γ-lactone moiety at the C-6, 7 position are called arnbrosanolides. The references of the total syntheses of ambrosanolides are shown below: (a) Marshall, J. A.; Snyder, W. R. J. Org. Chem. 1975, 40, 1656. This paper did not report the total synthesis of ambrosanolides but described important synthetic methodology of ambrosanolides. (b) Kretchmer, R. A.; Thompson, W. J. J. Am. Chem. Soc. 1976, 98, 3379. (c) DeClercq, P.; Vandewalle, M. J. Org. Chem. 1977, 42, 3447. (d) Kok, P.; DeClercq, P.; Vandewalle, M. Bull. Soc. Chem. Belg. 1978, 87, 615. (e) Grieco, P. A.; Ohfune, Y.; Majetich, G. J. Am. Chem. Soc. 1977, 99, 7393. (f) Grieco, P. A.; Oguri, T.; Burke, S.; Rodriguez, E.; DeTitta, G. T.; Fortier, S. J. Org. Chem. 1978, 43, 4552. (g) Roberts, M. R.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7626. Quallich, G. J.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7627. (h) Demuynck, M.; DeClercq, P.; Vandewalle, M. J. Org. Chem. 1979, 44, 4863. Heathcock, C. H.; Tice, C. M.; Germorth, T. C. J. Am. Chem. Soc. 1982, 104, 6081.
33. The pseudoguaianolides which possess the β-oriented secondary methyl group at C-10 and the cis-fused γ-lactone moiety at the C-6, 7 position are called arnbrosanolides. The references of the total syntheses of ambrosanolides are shown below: (a) Marshall, J. A.; Snyder, W. R. J. Org. Chem. 1975, 40, 1656. This paper did not report the total synthesis of ambrosanolides but described important synthetic methodology of ambrosanolides. (b) Kretchmer, R. A.; Thompson, W. J. J. Am. Chem. Soc. 1976, 98, 3379. (c) DeClercq, P.; Vandewalle, M. J. Org. Chem. 1977, 42, 3447. (d) Kok, P.; DeClercq, P.; Vandewalle, M. Bull. Soc. Chem. Belg. 1978, 87, 615. (e) Grieco, P. A.; Ohfune, Y.; Majetich, G. J. Am. Chem. Soc. 1977, 99, 7393. (f) Grieco, P. A.; Oguri, T.; Burke, S.; Rodriguez, E.; DeTitta, G. T.; Fortier, S. J. Org. Chem. 1978, 43, 4552. (g) Roberts, M. R.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7626. Quallich, G. J.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7627. (h) Demuynck, M.; DeClercq, P.; Vandewalle, M. J. Org. Chem. 1979, 44, 4863. Heathcock, C. H.; Tice, C. M.; Germorth, T. C. J. Am. Chem. Soc. 1982, 104, 6081.
34. The pseudoguaianolides which possess the β-oriented secondary methyl group at C-10 and the cis-fused γ-lactone moiety at the C-6, 7 position are called arnbrosanolides. The references of the total syntheses of ambrosanolides are shown below: (a) Marshall, J. A.; Snyder, W. R. J. Org. Chem. 1975, 40, 1656. This paper did not report the total synthesis of ambrosanolides but described important synthetic methodology of ambrosanolides. (b) Kretchmer, R. A.; Thompson, W. J. J. Am. Chem. Soc. 1976, 98, 3379. (c) DeClercq, P.; Vandewalle, M. J. Org. Chem. 1977, 42, 3447. (d) Kok, P.; DeClercq, P.; Vandewalle, M. Bull. Soc. Chem. Belg. 1978, 87, 615. (e) Grieco, P. A.; Ohfune, Y.; Majetich, G. J. Am. Chem. Soc. 1977, 99, 7393. (f) Grieco, P. A.; Oguri, T.; Burke, S.; Rodriguez, E.; DeTitta, G. T.; Fortier, S. J. Org. Chem. 1978, 43, 4552. (g) Roberts, M. R.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7626. Quallich, G. J.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7627. (h) Demuynck, M.; DeClercq, P.; Vandewalle, M. J. Org. Chem. 1979, 44, 4863. Heathcock, C. H.; Tice, C. M.; Germorth, T. C. J. Am. Chem. Soc. 1982, 104, 6081.
35. The pseudoguaianolides which possess the β-oriented secondary methyl group at C-10 and the cis-fused γ-lactone moiety at the C-6, 7 position are called arnbrosanolides. The references of the total syntheses of ambrosanolides are shown below: (a) Marshall, J. A.; Snyder, W. R. J. Org. Chem. 1975, 40, 1656. This paper did not report the total synthesis of ambrosanolides but described important synthetic methodology of ambrosanolides. (b) Kretchmer, R. A.; Thompson, W. J. J. Am. Chem. Soc. 1976, 98, 3379. (c) DeClercq, P.; Vandewalle, M. J. Org. Chem. 1977, 42, 3447. (d) Kok, P.; DeClercq, P.; Vandewalle, M. Bull. Soc. Chem. Belg. 1978, 87, 615. (e) Grieco, P. A.; Ohfune, Y.; Majetich, G. J. Am. Chem. Soc. 1977, 99, 7393. (f) Grieco, P. A.; Oguri, T.; Burke, S.; Rodriguez, E.; DeTitta, G. T.; Fortier, S. J. Org. Chem. 1978, 43, 4552. (g) Roberts, M. R.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7626. Quallich, G. J.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7627. (h) Demuynck, M.; DeClercq, P.; Vandewalle, M. J. Org. Chem. 1979, 44, 4863. Heathcock, C. H.; Tice, C. M.; Germorth, T. C. J. Am. Chem. Soc. 1982, 104, 6081.
36. The pseudoguaianolides which possess the β-oriented secondary methyl group at C-10 and the cis-fused γ-lactone moiety at the C-6, 7 position are called arnbrosanolides. The references of the total syntheses of ambrosanolides are shown below: (a) Marshall, J. A.; Snyder, W. R. J. Org. Chem. 1975, 40, 1656. This paper did not report the total synthesis of ambrosanolides but described important synthetic methodology of ambrosanolides. (b) Kretchmer, R. A.; Thompson, W. J. J. Am. Chem. Soc. 1976, 98, 3379. (c) DeClercq, P.; Vandewalle, M. J. Org. Chem. 1977, 42, 3447. (d) Kok, P.; DeClercq, P.; Vandewalle, M. Bull. Soc. Chem. Belg. 1978, 87, 615. (e) Grieco, P. A.; Ohfune, Y.; Majetich, G. J. Am. Chem. Soc. 1977, 99, 7393. (f) Grieco, P. A.; Oguri, T.; Burke, S.; Rodriguez, E.; DeTitta, G. T.; Fortier, S. J. Org. Chem. 1978, 43, 4552. (g) Roberts, M. R.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7626. Quallich, G. J.; Schlessinger, R. H. J. Am. Chem. Soc. 1979, 101, 7627. (h) Demuynck, M.; DeClercq, P.; Vandewalle, M. J. Org. Chem. 1979, 44, 4863. Heathcock, C. H.; Tice, C. M.; Germorth, T. C. J. Am. Chem. Soc. 1982, 104, 6081.
37. Structure: Tapiolas, D. M.; Roman, M.; Fenical, W.; Stout, T. J.; Clardy, J. J. Am. Chem. Soc. 1991, 113, 4682.
38. Syntheses: (a) Buszek, K. R.; Sato, N.; Jeong, Y. J. Am. Chem. Soc. 1994, 116, 5511. (b) McWilliams, J. C.; Clardy, J. J. Am. Chem. Soc. 1994, 116, 8378. (c) Bach, J.; Berenguer, R.; Garcia, J.; Vilarrasa, J. Tetrahedron Lett. 1995, 3425. (d) Buszek, K. R.; Jeong, Y. Tetrahedron Lett. 1995, 7189. (e) Andrus, M. B.; Argade, A. B. Tetrahedron Lett. 1996, 5049. (f) Kodama, M.; Matsushita, M.; Terada, Y.; Takeuchi, A.; Yoshio, S.; Fukuyama, Y. Chem. Lett. 1997, 117.
39. Syntheses: (a) Buszek, K. R.; Sato, N.; Jeong, Y. J. Am. Chem. Soc. 1994, 116, 5511. (b) McWilliams, J. C.; Clardy, J. J. Am. Chem. Soc. 1994, 116, 8378. (c) Bach, J.; Berenguer, R.; Garcia, J.; Vilarrasa, J. Tetrahedron Lett. 1995, 3425. (d) Buszek, K. R.; Jeong, Y. Tetrahedron Lett. 1995, 7189. (e) Andrus, M. B.; Argade, A. B. Tetrahedron Lett. 1996, 5049. (f) Kodama, M.; Matsushita, M.; Terada, Y.; Takeuchi, A.; Yoshio, S.; Fukuyama, Y. Chem. Lett. 1997, 117.
40. Syntheses: (a) Buszek, K. R.; Sato, N.; Jeong, Y. J. Am. Chem. Soc. 1994, 116, 5511. (b) McWilliams, J. C.; Clardy, J. J. Am. Chem. Soc. 1994, 116, 8378. (c) Bach, J.; Berenguer, R.; Garcia, J.; Vilarrasa, J. Tetrahedron Lett. 1995, 3425. (d) Buszek, K. R.; Jeong, Y. Tetrahedron Lett. 1995, 7189. (e) Andrus, M. B.; Argade, A. B. Tetrahedron Lett. 1996, 5049. (f) Kodama, M.; Matsushita, M.; Terada, Y.; Takeuchi, A.; Yoshio, S.; Fukuyama, Y. Chem. Lett. 1997, 117.
41. Syntheses: (a) Buszek, K. R.; Sato, N.; Jeong, Y. J. Am. Chem. Soc. 1994, 116, 5511. (b) McWilliams, J. C.; Clardy, J. J. Am. Chem. Soc. 1994, 116, 8378. (c) Bach, J.; Berenguer, R.; Garcia, J.; Vilarrasa, J. Tetrahedron Lett. 1995, 3425. (d) Buszek, K. R.; Jeong, Y. Tetrahedron Lett. 1995, 7189. (e) Andrus, M. B.; Argade, A. B. Tetrahedron Lett. 1996, 5049. (f) Kodama, M.; Matsushita, M.; Terada, Y.; Takeuchi, A.; Yoshio, S.; Fukuyama, Y. Chem. Lett. 1997, 117.
42. Syntheses: (a) Buszek, K. R.; Sato, N.; Jeong, Y. J. Am. Chem. Soc. 1994, 116, 5511. (b) McWilliams, J. C.; Clardy, J. J. Am. Chem. Soc. 1994, 116, 8378. (c) Bach, J.; Berenguer, R.; Garcia, J.; Vilarrasa, J. Tetrahedron Lett. 1995, 3425. (d) Buszek, K. R.; Jeong, Y. Tetrahedron Lett. 1995, 7189. (e) Andrus, M. B.; Argade, A. B. Tetrahedron Lett. 1996, 5049. (f) Kodama, M.; Matsushita, M.; Terada, Y.; Takeuchi, A.; Yoshio, S.; Fukuyama, Y. Chem. Lett. 1997, 117.
43. Syntheses: (a) Buszek, K. R.; Sato, N.; Jeong, Y. J. Am. Chem. Soc. 1994, 116, 5511. (b) McWilliams, J. C.; Clardy, J. J. Am. Chem. Soc. 1994, 116, 8378. (c) Bach, J.; Berenguer, R.; Garcia, J.; Vilarrasa, J. Tetrahedron Lett. 1995, 3425. (d) Buszek, K. R.; Jeong, Y. Tetrahedron Lett. 1995, 7189. (e) Andrus, M. B.; Argade, A. B. Tetrahedron Lett. 1996, 5049. (f) Kodama, M.; Matsushita, M.; Terada, Y.; Takeuchi, A.; Yoshio, S.; Fukuyama, Y. Chem. Lett. 1997, 117.
44. Nozoe, T.; Takase, K.; Kato, M.; Nogi, T. Tetrahedron 1971, 27, 6023.
45. Brady, W. T.; Hieble, J. P. J. Am. Chem. Soc. 1972, 94, 4278.
46. Brady, W. T. Synthesis 1971, 415.
47. We have already completed the syntheses of two ambrosanolides, hymenolin and parthenin from the intermediate C, and the synthesis of the C-1-C-8 part of octalactins A and B (formal total syntheses of these compounds) from intermediate B. These results will appear in the following papers of this series.
48. Ando, M.; Kataoka, N.; Yasunami, M.; Takase, K.; Hirata, N.; Yanagi, Y. J. Org. Chem. 1987, 52, 1429.
49. Barton, D. H. R.; McCombie, S. W. J. Chem. Soc., Perkin Trans. 1 1975, 1574.
50. Dale, J. A.; Mosher, H. S. J. Am. Chem. Soc. 1973, 95, 512.
51. 0 = cell count at the start of culture.
52. Test samples, which were formulated as emulsifiable in water, were applied by spraying to the plants or drenching to soil before or after incubation. The plants were inoculated with spores or hypa of ningal pathogens. After incubation, disease severity of test plants was observed under desirable conditions for 4-15 days. The tested crop diseases are as follows; blast of rice, sheath blight of rice, powdery mildew of wheat, damping off of cucumber, dawny mildew of grape, late blight of tomato, scab of apple.
53. In 8-10 days after sowing, test samples, which were formulated as emulsifiable in water, were applied by spraying to the plants and the degree of the growth inhibition of plants was observed.