Studies toward funiculosin. Intramolecular carbonyl condensations using carboxamidimidazolide intermediates

Tetrahedron Letters

Volumn 38, Issue 3, 1997, Pages 327-330

  Williams, David R ^a   Lowder, Patrick D ^a   Yu Gui, Gu ^a  

^a INDIANA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANTIFUNGAL AGENT; ANTINEOPLASTIC AGENT; ANTIVIRUS AGENT; FUNICULOSIN;

ARTICLE; DRUG SYNTHESIS; INFRARED SPECTROPHOTOMETRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0031031179     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(96)02343-X     Document Type: Article

References (24)

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8. For studies of pyridin-2-ones as C-linked deoxyribosides: Solomon, M.S.; Hopkins, P.B.; Tetrahedron Lett. 1991, 32, 3297. Bothwick, A.D.; Biggadike, K.; Paternoster, I.L.; Coates, J.A.V.; Knight, D.J. Bioorg. Med. Chem. Lett. 1993, 2577.
9. For studies of pyridin-2-ones as C-linked deoxyribosides: Solomon, M.S.; Hopkins, P.B.; Tetrahedron Lett. 1991, 32, 3297. Bothwick, A.D.; Biggadike, K.; Paternoster, I.L.; Coates, J.A.V.; Knight, D.J. Bioorg. Med. Chem. Lett. 1993, 2577.
10. For another route to the all-syn-cyclopentanetetrol: Begley, M.J.; Madeley, J.P.; Pattenden, G.; Smith, G.F. J. Chem. Soc. Perkin I, 1992, 57.
11. Williams, D.R.; Sit, S.-Y. J. Org. Chem. 1982, 47, 2846. Williams, D.R.; Bremmer, M.L.; Brown, D.L.; D'Antuono, J. J. Org. Chem. 1985, 50, 2807.
12. Williams, D.R.; Sit, S.-Y. J. Org. Chem. 1982, 47, 2846. Williams, D.R.; Bremmer, M.L.; Brown, D.L.; D'Antuono, J. J. Org. Chem. 1985, 50, 2807.
13. For other approaches: Rigby, J.H.; Qabar, M. J. Org. Chem. 1989, 54, 5852. Buck, J.; Madeley, J.P.; Pattenden, G. J. Chem. Soc. Perkin I, 1992, 67.
14. For other approaches: Rigby, J.H.; Qabar, M. J. Org. Chem. 1989, 54, 5852. Buck, J.; Madeley, J.P.; Pattenden, G. J. Chem. Soc. Perkin I, 1992, 67.
15. Malachowski, R.; Prebendowski, S. Chem. Ber. 1938, 71, 2241. For synthesis of croconic acid: Gmelin, L. Ann. der Physik. 1825, 4, 31. Croconate esters are unstable and undergo facile hydrolysis to the nonbenzenoid aromatic dianion: West, R. Oxocarbons, Academic Press, New York, (1980), Chapter 1, pages 1-14.
16. Malachowski, R.; Prebendowski, S. Chem. Ber. 1938, 71, 2241. For synthesis of croconic acid: Gmelin, L. Ann. der Physik. 1825, 4, 31. Croconate esters are unstable and undergo facile hydrolysis to the nonbenzenoid aromatic dianion: West, R. Oxocarbons, Academic Press, New York, (1980), Chapter 1, pages 1-14.
17. Malachowski, R.; Prebendowski, S. Chem. Ber. 1938, 71, 2241. For synthesis of croconic acid: Gmelin, L. Ann. der Physik. 1825, 4, 31. Croconate esters are unstable and undergo facile hydrolysis to the nonbenzenoid aromatic dianion: West, R. Oxocarbons, Academic Press, New York, (1980), Chapter 1, pages 1-14.
18. 2; reflux for 45 min) at a much faster rate (100% yield) than lactonization of the anti-hydroxyester (catalytic TsOH; benzene; reflux; two hrs; 84% yield). The lactone 7 was decomposed by extending reaction times.
19. Reduction with 5% rhodium on alumina (Aldrich) at room temperature with 1900 psi hydrogen (48 hrs) gave 8 in 82% yield. Moderate hydrogen pressures (50-100 psi) were also effective, but less reproducible, and were accompanied by small quantities of elimination side products. Direct hydrogenation of 4, 5 or 6 gave complex mixtures.
20. 3, permitted competing formation of the five-membered ethyl acetal formed via hydrolysis of one MOM ether.
21. Staab, H.A. Angew. Chem. Int. Ed. Engl. 1962, 1, 351.
22. -1 in their infrared spectra. Proton and carbon NMR data indicated that these β-keto amides exist as their carbonyl tautomers with no evidence for enol isomers. The final pyridinones 2 are characterized solely as C-4 enols.
23. For discussion of the use of bromotrichloromethane as an oxidant for heterocycle synthesis: Williams, D.R.; Lowder, P.D.; Gu, Y.-G.; Brooks, D.A. Tetrahedron Lett. 1996, 37, (immediately follows this communication).
24. Isolated yields are reported for purified products which were fully characterized by proton and carbon NMR spectra, infrared, and high-resolution mass spectrometry. Combustion analyses data were used to check one third of the compounds in the synthesis sequence.