A β-lactone-based strategy applied to the total synthesis of (8S,21S,22S,23R)- and (8R,21S,22S,23R)-okinonellin B

Journal of Organic Chemistry

Volumn 63, Issue 7, 1998, Pages 2058-2059

  Schmitz, William D ^a   Messerschmidt, N Brian ^a   Romo, Daniel ^a  

^a TEXAS A AND M UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

LACTONE; NATURAL PRODUCT; OKINONELLIN B; UNCLASSIFIED DRUG;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL REACTION; CHEMICAL STRUCTURE; DRUG SYNTHESIS; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY;

EID: 0032478666     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9722360     Document Type: Article

References (31)

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2. We are aware of only a few examples of the use of β-lactones as intermediates in asymmetric, natural product total synthesis: (a) Bourgeanic Acid: White, J. D.; Johnson, A. T. J. Org. Chem. 1994, 59, 3347-3358. (b) Lactacystin: Corey, E. J.; Reichard, G. A.; Kania, R. Tetrahedron Lett. 1993, 34, 6977-6980.
3. We are aware of only a few examples of the use of β-lactones as intermediates in asymmetric, natural product total synthesis: (a) Bourgeanic Acid: White, J. D.; Johnson, A. T. J. Org. Chem. 1994, 59, 3347-3358. (b) Lactacystin: Corey, E. J.; Reichard, G. A.; Kania, R. Tetrahedron Lett. 1993, 34, 6977-6980.
4. For some recent asymmetric methods for β-lactone synthesis, see: Yang, H. W.; Romo, D. J. Org. Chem. 1998, 63, 1344-1347 and references therein.
5. Kato, Y.; Fusetani, N.; Matsugaga, S.; Hashimoto, K. Experientia 1986, 42, 1299.
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15. 2: Bernasconi, S.; Colombo, M.; Jommi, G.; Sisti, M. Gass. Chem. Ital. 1986, 116, 69-71.
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18. Lactone 13 is available in four steps from (-)-malic acid; see: Bernardi, A.; Cardani, S.; Scolastico, C.; Villa, R. Tetrahedron 1990, 46, 1987-1998.
19. Best results were obtained after titration of the generated Grignard reagent; see: Bergbreiter, D. E.; Pendergrass, E. J. Org. Chem. 1981, 46, 219-220.
20. 2.
21. Tebbe, F. N.; Parshall, G. W.; Reddy, G. S. J. Am. Chem. Soc. 1978, 100, 3611-3613.
22. 1H NMR).
23. An interesting byproduct i was obtained (5-10%) in the TMAL reaction. We are currently studying this presumed Zn(II) (or trace metal)-mediated reaction. For possible related palladium- and ruthenium-mediated processes, see: Trost, B. M., Tanoury, G. J. J. Am. Chem. Soc. 1988, 110, 1636-1638. Chatani, N.; Morimoto, T.; Muto, T.; Murai, S. J. Am. Chem. Soc. 1994, 116, 6049-6050.
24. An interesting byproduct i was obtained (5-10%) in the TMAL reaction. We are currently studying this presumed Zn(II) (or trace metal)-mediated reaction. For possible related palladium- and ruthenium-mediated processes, see: Trost, B. M., Tanoury, G. J. J. Am. Chem. Soc. 1988, 110, 1636-1638. Chatani, N.; Morimoto, T.; Muto, T.; Murai, S. J. Am. Chem. Soc. 1994, 116, 6049-6050.
25. The enantiomeric purity was determined by chiral HPLC (Chiralcel OD) on comparison to the racemic β-lactone. See the Supporting Information for details.
26. Our current mechanistic understanding of the Zn(II)-mediated TMAL reaction will be described in a separate report: Zhao, C.; Yang, H. W.; Romo, D. Manuscript in preparation.
27. Wipf, P.; Lim, S. Angew. Chem., Int. Ed. Engl. 1993, 32, 1068-1071.
28. Farina, V.; Krishnan, B. J. Am. Chem. Soc. 1991, 113, 9585-9595.
29. It was noted that complete consumption of the vinyl iodide 3 occurred rapidly during the reaction, and a byproduct derived from this material was the methylated olefin ii. As a result, substantial amounts of the olefin iii were obtained on quenching the reaction. In a separate experiment, the vinyl iodide iv could be obtained in 57% yield by iodinolysis. For a lead reference to related reactions of vinyl triflates, see: Saulnier, M.; Kadow, J.; Tun, M. M.; Langley, D.; Vyas, D. J. Am. Chem. Soc. 1989, 111, 8320-8321.
30. An authentic sample of okinonellin B was no longer available as it had degraded. In addition, recent re-extraction of the sponge did not afford any detectable okinonellin B (private communication from N. Fusetani and S. Matsunaga, University of Tokyo). We have also noted the instability of okinonellin B even when frozen in benzene.
31. D = -98.0 (c 0.15, EtOH).