The First Transformation of Aliphatic αβ-Epoxyamides into α-Hydroxyamides

Organic Letters

Volumn 5, Issue 25, 2003, Pages 4783-4785

  Concellón, José M ^a   Bardales, Eva ^a  

^a UNIVERSITY OF OVIEDO   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ALIPHATIC COMPOUND; AMIDE; EPOXIDE; HYDROXIDE; SAMARIUM DIIODIDE;

ARTICLE; CHEMICAL BOND; DRUG SYNTHESIS; ENANTIOMER; REACTION ANALYSIS; REDUCTION;

AMIDES; EPOXY COMPOUNDS; IODIDES; MOLECULAR STRUCTURE; SAMARIUM; STEREOISOMERISM;

EID: 0345791432     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol035757k     Document Type: Article

References (22)

1. Studies in Natural Products Chemistry; Atta-ur-Rahman, Ed.; Elsevier: 1988; Vol. 2, p 680.
2. Markaverich, B. M.; Gregory, R. R.; Alejandro, M. A.; Kittrell, K. S.; Medina, D.; Clark, J. H.; Varma, M.; Varma, R. S. Cancer Res. 1990, 50, 1470-1478.
3. α-Hydroxy Acids in Enantioselective Syntheses; Coppola, G. M., Schuster, H. F., Eds.; VCH: Weinheim, 1997.
4. (a) Johnson, H. E.; Grosby, D. J. Org. Chem. 1963, 28, 3255-3256.
5. (b) Grison, C.; Coutrot, F.; Comoy, C.; Lemilbeau, C.; Coutrot, P. Tetrahedron Lett. 2000, 41, 6571-6574.
6. Nemoto, T.; Kakei, H.; Gnanadesikan, V.; Tosaki, S.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2002, 124, 14544-14545.
7. Molander, G. A.; Hahn, G. J. Org. Chem. 1986, 51, 2596-2599.
8. (a) Otsubo, K.; Inanaga, J.; Yamaguchi, M. Tetrahedron Lett. 1987, 28, 4437-4440.
9. (b) Molander, G. A.; La Belle, B. E.; Hahn, G. J. Org. Chem. 1986, 51, 5259-5264.
10. (c) Reetz, M. T.; Lauterbach, E. H. Tetrahedron Lett. 1991, 32, 4477-4480.
11. Concellón, J. M.; Bardales, E. Tetrahedron Lett. 2003, 44, 5323-5326.
12. 2 were used, the α- hydroxyamides obtained were contaminated with other products of radical coupling.
13. 2 in THF was rapidly obtained by reaction of diiodomethane with samarium powder in the presence of sonic waves: Concellón, J. M.; Rodriguez-Solla, H.; Bardales, E.; Huerta, M. Eur. J. Org. Chem. 2003, 1775-1778.
14. 2 (1.6 mmol) and MeOH (0.5 mL) in THF (19 mL) was added, under a nitrogen atmosphere, to a stirred solution of aliphatic α,β- epoxyamide 1 (0.4 mmol) in THF (2 mL) at 25°C. The mixture was stirred for 3 h at this temperature and then quenched with aqueous HCl (0.1 M, 15 mL). Usual workup afforded crude 2-hydroxyamides 2, which were purified by flash column chromatography on silica gel (hexane/AcOEt).
15. Disubstituted epoxyamide compounds 1a-c were prepared by reaction of the lithium enolate of chloroacetamide with the correspondig aldehyde and further treatment with sodium hydride. See Supporting Information.
16. Isotope-labeled compounds are very useful for establishing the mechanism of organic reactions and the biosynthesis of many natural compounds: Mann, J. Secondary Metabolism; Oxford University Press: Oxford, 1986; p 23.
17. Results of the synthesis of dimerization products are being studied.
18. Molander, L.; Saunders, W. H. Reaction Rates of Isotopic Molecules; Wiley: New York, 1980.
19. Similar radical mechanism is proposed for the opening of epoxides promoted by titanium III: RajanBabu, T. B.; Nugent, W. A. J Am. Chem. Soc. 1994, 116, 986-997.
20. Gau, Y.; Hanson, R. M.; Klunder, J. M.; Ko, S. Y.; Masamune, H.; Sharpless, K. B. J. Am. Chem. Soc. 1987, 65, 5765-5779.
21. Huang, D. F.; Huang, L. Tetrahedron 1990, 46, 3135-3142.
22. Estiarte, M. A.; Rubiralta, M.; Diez, A. J. Org. Chem. 2002, 67, 6992-6999.