The Convergent Synthesis of Polyether Ionophore Antibiotics: The Synthesis of the Monensin Bis(tetrahydrofuran) via the Claisen Rearrangement of an Ester Enolate with a β-Leaving Group

Journal of the American Chemical Society

Volumn 107, Issue 11, 1985, Pages 3279-3285

  Ireland, Robert E ^a   Norbeck, Daniel W ^a  

^a CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

MONENSIN DERIVATIVE;

DRUG ANALYSIS; DRUG IDENTIFICATION; DRUG SYNTHESIS; INFRARED SPECTROMETRY; MASS SPECTROMETRY; NONHUMAN; NUCLEAR MAGNETIC RESONANCE; PRIORITY JOURNAL; THEORETICAL STUDY;

EID: 0021934691     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00297a038     Document Type: Article

References (20)

1. For the structure of monensin and the synthesis of its spiroketal subunit, see: Ireland, R. E.; Habich, D.; Norbeck, D. W. J. Am. Chem. Soc. preceding paper in this issue.
2. Ireland, R. E.; Wilcox, C. S.; Thaisrivongs, S.; J. Org. Chem. 1978, 43, 786–787. Ireland, R. E.; Thaisrivongs, S.; Vanier, N.; Wilcox, C. S. J. Org. Chem. 1980, 45, 48–61. Ireland, R. E.; Wilcox, C. S.; Thaisrivongs, S.; Varnier, N. R. Can. J. Chem. 1979, 57, 1743–1745. Ireland, R. E.; Vevert, J.-P. Can. J. Chem. 1981, 59, 572–583. Ireland, R. E.; Vevert, J.-P. J. Org. Chem. 1980, 45, 4259–4260.
3. Brimacombe, J. S.; Hunedy, F.; Tucket, L. C. N. J. Chem. Soc. C 1968, 1381–1384.
4. Ficini, J.; Depezay, J.-C. Tetrahedron Lett. 1968, 937–942. Still, W. C.; Schneider, M. J. J. Am. Chem. Soc. 1977, 99, 948–950.
5. Seebach, D. In “Modern Synthetic Methods-1980“; Scheffold, R., Ed.; Otto Salle Verlag:Frankfurt, 1980; pp 132–134. Barluenga, J.; Fañanás, F. J.; Yus, M. J. Org. Chem. 1979, 44, 4798–4801. Taschner, M. J.; Kraus, G. A. Tetrahedron Lett. 1977, 4575. Hermann, J. L.; Schlessinger, R. H. Tetrahedron Lett. 1973, 2429–2431. Fráter, G. Helv. Chim. Acta. 1979, 62, 2825–2828. Helv. Chim. Acta. 2829–2832. Seebach, D.; Wasmuth, D. Helv. Chim. Acta. 1980, 63, 197–200. Shieh, H.-M.; Prestwich, G. D. J. Org. Chem. 1981, 46, 4319–4321.
6. Smith, A. B.; Jerris, P. J. Synth. Commun. 1978, 8, 421. Mulzer, J.; Kerkmann, T. J. Am. Chem. Soc. 1980, 102, 3620–3622. Schöllkopf, U.; Hoppe, J. Angew. Chem., Int. Ed. Engl. 1975, 14, 765. Ladner, W. J. Angew. Chem., Int. Ed. Engl. 1982, 21, 449–450. Naef, R.; Seebach, D. J. Angew. Chem., Int. Ed. Engl. 1981, 20, 1030–1031. Williams, D. T.; Jones, J. K. N. Can. J. Chem. 1964, 42, 69. Ho, P. T. Can. J. Chem. 1979, 57, 381–383. Hoffmann, R. W.; Ladner, W. Chem. Ber. 1983, 116, 1631–1642. Lee, A. W. M.; Martin, V. S.; Masamune, S.; Sharpless, K. B.; Walker, F. J. J. Am. Chem. Soc. 1982, 104, 3515–3516. Baldwin, J. E. J. Chem. Soc., Chem. Commun. 1976, 734, 736, 738.
7. After completion of this work, similar in situ silylations were reported. Krizan, T. D.; Martin, J. C. J. Am. Chem. Soc. 1983, 105, 6155. Corey, E. J.; Gross, A. Tetrahedron Lett. 1984, 495–498.
8. For other instances of the successful utilization of carbanions with good β-leaving groups, see: Seyferth, D.; Mueller, D. C.; Armbrecht, F. M. Organomet. Chem. Synth. 1970/1971, 1, 3-6. Schlosser, M.; Ladenberger, V. Angew. Chem., Int. Ed. Engl. 1966, 5, 519. Ficini, J.; Depezay, J.-C. Tetrahedron Lett. 1969, 4797–4799. Ko, S. S.; Klein, L. L.; Pfaff, K.-S.; Kishi, Y. Tetrahedron Lett. 1982, 4415–4418. Schwiezer, E. E.; Creary, W. S.; Light, K. K.; Schaffer, E. T. J. Org. Chem. 1969, 34, 212. Secrist, J. A., III; Wu, S.-R. J. Org. Chem. 1977, 42, 4084; 1979, 44, 1434. Secrist, J. A., III; Barnes, K. D. J. Org. Chem. 1980, 45, 4526. Cousineau, T. J.; Cook, S. L.; Secrist, J. A., III. Synth. Commun. 1979, 9, 157.
9. Baker, R. R.; Schaub, R. E.; Williams, J. H. J. Am. Chem. Soc. 1955, 77, 7–12.
10. Miyashita, M.; Yoshikoshi, A.; Grieco, P. A. J. Org. Chem. 1977, 42, 3772.
11. Omura, K.; Swern, D. Tetrahedron 1978, 34, 1651–1660.
12. Collins, P. M.; Hurford, J. R.; Overend, W. O. J. Chem. Soc., Perkin. Trans. 1 1975, 2163–2177.
13. The stereochemical assignment was based on the smooth equilibration of the acetonide to the 2, 3 position. Inversion at C2 via a carbonium ion is not likely under the mild conditions used. Halford, M. H.; Ball, D. H.; Long, L., Jr. Carbohydr. Res. 1968, 8, 363–365.
14. Clode, D. M. Chem. Rev. 1979, 79, 491–513. TLC suggests that the equilibration proceeds through the triol.
15. [2-(Trimethylsilyl)ethoxy]methyl chloride (SEM-C1): Lipshutz, B. H.; Pegram, J. J. Tetrahedron Lett. 1980, 3343–3346. Allyl ether: Gigg, R.; Warren, C. D. J. Chem. Soc. C 1968, 1903–1911.
16. Ireland, R. E.; Mueller, R. H. J. Am. Chem. Soc. 1972, 94, 5897–5898. Ireland, R. E.; Mueller, R. H.; Willard, A. K. J. Am. Chem. Soc. 1976, 98, 2868–2877.
17. Ireland, R. E.; Norbeck, D. W.; Mandel, G. S.; Mandel, N. S. J. Am. Chem. Soc., following paper in this issue.
18. Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem., 1978, 43, 2923.
19. Ireland, R. E.; Anderson, R. C.; Badoud, R.; Fitzsimmons, B. J.; McGarvey, G. J.; Thaisrivongs, S.; Wilcox, C. S. J. Am. Chem. Soc. 1983, 105, 1988–2006.
20. Silver oxide: Shamma, M.; Rodriguez, H. R. Tetrahedron 1968, 24, 6583–6589. No epimerization was detected under these conditions. Reduction of the methyl esters of 24 and 25 with LAH gave the starting alcohols.