A concise total synthesis of (±)-cis- and (±)-trans-clavicipitic acids by combinational use of directed lithiation and fluoride ion-induced elimination-addition reaction of 1-(triisopropylsilyl)gramine derivatives

Tetrahedron

Volumn 53, Issue 1, 1997, Pages 51-58

  Iwao, Masatomo ^a   Ishibashi, Fumito ^a  

^a NAGASAKI UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

AMINO ACID DERIVATIVE; CLAVICIPITIC ACID; ERGOT ALKALOID; UNCLASSIFIED DRUG;

ARTICLE; DRUG SYNTHESIS; NUCLEAR MAGNETIC RESONANCE; PRIORITY JOURNAL; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0031060425     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(96)00977-5     Document Type: Article

References (27)

1. a) Robbers, J. E.; Floss, H. G. Tetrahedron Lett. 1969, 1857.
2. b) King, G. S.; Mantle, P. G.; Szczyrbak, C. A.; Waight, E. S. Tetrahedron Lett. 1973, 215.
3. c) King, G. S.; Waight, E. S.; Mantle, P. G.; Szczyrbak, C. A. J. Chem. Soc., Perkin Trans. I 1977, 2099.
4. d) Robbers, J. E., Otsuka, H.; Floss, H. G.; Arnold, E. V.; Clardy, J. J. Org. Chem. 1980, 45, 1117.
5. a) Kozikowski, A. P.; Greco, M. N. Heterocycles 1982, 19, 2269.
6. b) Muratake, H; Takahashi, T.; Natsume, M. Heterocycles 1983, 20, 1963.
7. c) Kozikowski, A. P.; Greco, M. N. J. Org. Chem. 1984, 49, 2310.
8. d) Kozikowski, A. P.; Okita, M. Tetrahedron Lett. 1985, 26, 4043.
9. e) Matsumoto, M.; Kobayashi, H.; Watanabe, N. Heterocycles 1987, 26, 1197.
10. f) Harrington, P. J.; Hegedus, L. S.; McDaniel, K. F. J. Am Chem. Soc. 1987, 109, 4335.
11. g) Boyles, D. A.; Nichols, D. E. J. Org. Chem. 1988, 53, 5128.
12. h) Somei, M.; Hamamoto, S.; Nakagawa, K.; Yamada, F.; Ohta, T. Heterocycles 1994, 37, 719.
13. i) Yokoyama, Y.; Matsumoto, F.; Murakami, Y. J. Org. Chem. 1995, 60, 1486.
14. Iwao, M. Heterocycles 1993, 36, 29.
15. Iwao, M.; Motoi, O. Tetrahedron Lett. 1995, 36, 5929.
16. a) Snyder, C. D.; Bondinell, W. E.; Rapoport, H. J. Org. Chem. 1971, 36, 3951.
17. b)Wenkert, E.; Moeller, P. D. R.; Piettre, S. R.; McPhail, A. T. J. Org. Chem. 1988, 53, 3170.
18. c) Ballester, P.; Capó, M.; Garcías, X.; Saá, J. M. J. Org. Chem. 1993, 58, 328.
19. Tsushima, T.; Kawada, K. Tetrahedron Lett. 1985, 26, 2445.
20. Paik, Y.H.; Dowd, P. J. Org. Chem. 1986, 51, 2910.
21. For comparison, see: a) Plieninger, H.; Höbel, M.; Liede, V. Chem. Ber. 1963, 96, 1618.
22. b) Nettekoven, M.; Psiorz, M.; Waldmann, H. Tetrahedron Lett., 1995, 36, 1425.
23. Just, G.; Grozinger, K. Synthesis 1976, 457.
24. Miyashita, M.; Yoshikoshi, A.; Grieco, P. A. J. Org. Chem. 1977, 42, 3772.
25. 1H nmr spectra of (±)-cis-clavicipitic acid and (±)-trans-clavicipitic acid.
26. Cis -1a is only sparingly soluble in hot MeOH, while trans-1b is well soluble.
27. Relatively large gap between the melting point of 1b and the literature value is due to the difference of determination methods. Dr. H. Muratake (Research Foundation Itsuu Laboratory) kindly informed us that he measured the melting point by placing his sample between two cover glasses and heating it on a micro hot plate. We could not determine the accurate melting point by this way due to gradual decomposition of 1b over 200 °C.