Synthesis of (E)-α,β-unsaturated ketones with total or high diastereoselectivity by using samarium diiodide or triiodide

Tetrahedron Letters

Volumn 44, Issue 9, 2003, Pages 1931-1934

  Concellón, José M ^a   Huerta, Mónica ^a  

^a UNIVERSITY OF OVIEDO   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

AZIDE; KETONE DERIVATIVE; POTASSIUM HEXAMETHYLDISILAZIDE; SAMARIUM DIIODIDE; UNCLASSIFIED DRUG; UNSATURATED FATTY ACID;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL MODIFICATION; CHEMICAL REACTION; DIASTEREOISOMER; GAS CHROMATOGRAPHY; MASS SPECTROMETRY; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; SYNTHESIS;

EID: 0037463460     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(03)00079-0     Document Type: Article

References (27)

1. Patai S., Rappoport Z. The Chemistry of Enones. 1989;281-312 John Wiley & Sons.
2. Patai S., Rappoport Z. The Chemistry of Enones. 1989;199-280 John Wiley & Sons.
3. Maryanoff B.E., Reitz A.B. Chem. Rev. 89:1989;863-927.
4. Dauben W.G., Michno D.M. J. Org. Chem. 42:1977;682-685.
5. Reich H.J., Renga J.M., Reich I.L. J. Am. Chem. Soc. 97:1975;5434-5447.
6. Resek J.E., Meyers A.I. Tetrahedron Lett. 36:1995;7051-7054.
7. Schwarz I., Braun M. Chem. Eur. J. 5:1999;2300-2305.
8. Labadie J.W., Tueting D., Stille J.K. J. Org. Chem. 48:1983;4634-4642.
9. Mitchell T.N. Synthesis. 9:1992;803-815.
10. Negishi E., Swanson D.R., Cederbaum F.E., Takahashi T. Tetrahedron Lett. 28:1987;917-920.
11. Concellón, J. M.; Bernad, P. L.; Pérez-Andrés, J. A. Angew. Chem. 1999, 111, 2528-2530; Angew. Chem., Int. Ed. 1999, 38, 2384-2386.
12. Concellón, J. M.; Bernad, P. L.; Pérez-Andrés, J. A. Angew. Chem. 1999, 111, 2528-2530; Angew. Chem., Int. Ed. 1999, 38, 2384-2386.
13. Concellón J.M., Bardales E. Org. Lett. 4:2002;189-191.
14. Concellón J.M., Pérez-Andrés J.A., Rodríguez-Solla H. Chem. Eur. J. 7:2001;3062-3068.
15. Concellón J.M., Bernad P.L., Bardales E. Org. Lett. 3:2001;937-939.
16. Concellón, J. M.; Bernad, P.; Rodríguez-Solla, H. Angew. Chem. 2001, 113, 4015-4017; Angew. Chem., Int. Ed. 2001, 40, 3897-3899.
17. Concellón, J. M.; Bernad, P.; Rodríguez-Solla, H. Angew. Chem. 2001, 113, 4015-4017; Angew. Chem., Int. Ed. 2001, 40, 3897-3899.
18. α,β-Unsaturated esters or amides were obtained from 2-chloro-3-hydroxyesters or amides and samarium diiodide by using these reaction conditions.
19. 2] was added dropwise at -25°C. The reaction mixture was stirred at the same temperature over 2 h and then heated at reflux for 1 additional hour (the color changed from yellow to orange). The reaction mixture was quenched with 5 ml of 0.1 M HCl and the usual workup gave the crude α,β-unsaturated ketone. Purification by flash column chromatography over silica or by distillation afforded the pure compound 3.
20. Ghelfi F., Grandi R., Pagnoni U.M. J. Chem. Res. (S). 1:1988;200-201.
21. When 1a-c were prepared from epoxyketones 4 only the anti diastereoisomer was obtained, while both two diastereoisomers, as a mixture roughly 1:1, were isolated when 1a-d were obtained by aldol condensation.
22. Takahashi A., Shibasaki M. J. Org. Chem. 53:1988;1227-1231.
23. 2: (a) Molander, G. A.; Etter, J. B.; Zinke, P. W. J. Am. Chem. Soc. 1987, 109, 453-463; (b) Urban, D.; Skrydstrup, T.; Beau, J. M. J. Org. Chem. 1998, 63, 2507-2516.
24. 2: (a) Molander, G. A.; Etter, J. B.; Zinke, P. W. J. Am. Chem. Soc. 1987, 109, 453-463; (b) Urban, D.; Skrydstrup, T.; Beau, J. M. J. Org. Chem. 1998, 63, 2507-2516.
25. Imamoto T., Kutsumoto T., Yokoyama M. J. Chem. Soc., Chem. Commun. 1982;1042-1044.
26. 2) at -25°C during 2 h and later heated at reflux by 1 additional hour. The reaction was quenched with 5 ml of 0.1 M HCl, extracted with dichloromethane and concentrated. Purification by flash column chromatography or by distillation yielded the pure enone 3.
27. This intramolecular hydrolysis was previously observed in the transformation of 2-chloro-3-hydroxyesters into α,β-unsaturated esters, in which the double bond C=C is tetrasubstituted: see Ref. 9a.