Epoxidation of alkenes with bicarbonate-activated hydrogen peroxide [3]

Journal of the American Chemical Society

Volumn 122, Issue 13, 2000, Pages 3220-3221

  Yao, Huirong ^a   Richardson, David E ^a  

^a University of Florida ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; BICARBONATE; HYDROGEN PEROXIDE;

CARBON NUCLEAR MAGNETIC RESONANCE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; EPOXIDATION; LETTER; PROTON NUCLEAR MAGNETIC RESONANCE;

EID: 0034607292     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja993935s     Document Type: Letter

References (33)

1. (a) Rudolph, J.; Reddy, K. L.; Chiang, J. P.; Sharpless, K. B. J. Am. Chem. Soc. 1997, 119, 6189.
2. (b) Herrmann, W. A.; Ding, H.; Kratzer, R. M.; Kühn, F. E.; Haider, J. J.; Fischer, R. W. J. Organomet. Chem. 1997, 549, 319.
3. Sheldon, R. A. Top. Curr. Chem. 1993, 164, 21-34.
4. (a) Strukul, G. Catalytic Oxidation with Hydrogen Peroxide as Oxidant; Kluwer: Dordrecht, 1992.
5. (b) Młochowski, J.; Said, S. B. Pol. J. Chem. 1997, 71, 149.
6. Edwards, J. O. In Peroxide Reaction Mechanisms; Edwards, J. O., Ed.; Interscience: New York, 1962; pp 67-106.
7. Jacobson, E. N. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G., Wilkinson, E., Eds.; Pergamon: New York, 1995; Vol. 12, p 1097.
8. (a) Tetzlaff, H. R.; Espenson, J. H. Inorg. Chem. 1999, 38, 881.
9. (b) Venturello, C.; Alneri, E.; Ricci, M. J. Org. Chem. 1983, 48, 3831.
10. (c) De Vos, D. E.; Sels, B. F.; Reynaers, M.; Rao, Y. V. S.; Jacobs, P. A. Tetrahedron Lett. 1998, 39, 3221.
11. (a) Swern, D. In Organic Peroxides; Swern, D., Ed.; Wiley-Interscience: New York, 1971; Vol. 2, p 355.
12. (b) Lewis, S. H. In Oxidation; Augustine, R. L., Ed.; Marcel-Dekker: New York, 1969; Vol. I, p 213.
13. Payne, G. B.; Deming, P. H.; Williams, P. H. J. Org. Chem. 1961, 26, 659.
14. Majetich, G.; Hicks, R. Synlett 1996, 649.
15. McKillop, A.; Sanderson, W. R. Tetrahedron 1995, 51, 6145.
16. Drago, R. S.; Frank, K. M.; Yang, Y.-C.; Wagner, G. W. Proceedings of 1997 ERDEC Scientific Conference on Chemical and Biological Defense Research; ERDEC, 1998.
17. Richardson, D. E.; Yao, H.; Xu, C.; Drago, R. S.; Frank, K. M.; Wagner, G. W.; Yang, Y.-C. Proceedings of 1998 ERDEC Scientific Conference on Chemical and Biological Defense Research; ECBC, 1999.
18. Richardson, D. E.; Yao, H.; Frank, K. M.; Bennett, D. J. Am. Chem. Soc. 2000, 122, in press.
19. (a) Flanagan, J.; Jones, D. P.; Griffith, W. P.; Skapski, A. C.; West, A. P. J. Chem. Soc., Chem. Commun. 1986, 20-21.
20. (b) Jones, D. P.; Griffith, W. P. J. Chem. Soc., Dalton Trans. 1980, 2526-2532.
21. (c) Adam, A.; Mehta, M. Angew. Chem., Int. Ed. 1998, 37, 1387-1388.
22. Although used in large concentrations, bicarbonate is a catalyst so the oxidations described here are low E factor reactions, in contrast to stoichiometric activators where a leaving group becomes a byproduct. See Sheldon, R. A. J. Chem. Technol. Biotechnol. 1997, 68, 381.
23. (a) Prat, D.; Lett, R. Tetrahedron Lett. 1986, 27, 707.
24. (b) Prat, D.; Delpech, B. Lett, R. Tetrahedron Lett. 1986, 27, 711.
25. (c) Stevens, H. C.; Kamen, A. J. J. Am. Chem. Soc. 1965, 87, 734.
26. Conversion rates are lower in mixed organic/aqueous solvents, in part because bicarbonate solubility decreases and less catalyst can be used; however, bicarbonate salts with alkylated ammonium cations can be used to increase catalyst solubility (Yao, H.; Richardson, D. E., work in progress).
27. 2 (30%, 360 mmol) were dissolved in 130 mL water, mixed with 240 mL of acetonitrile, and 4 mL of styrene (35 mmol) was added. The rt reaction was allowed to proceed in the dark without stirring for 24 h. The reaction mixture was diluted with 200 mL of water and extracted with chloroform (5 × 200 mL). The filtrate was washed with water (2 × 40 mL), dried, and concentrated by removal of solvent. Fractional distillation of the crude product gave 3.1 g of styrene oxide (75%).
28. 9 The best solvents for the DCC-activated epoxidation are hydroxylic ones such as methanol, ethanol or 2-propanol (except pure water).
29. 4 to maintain similar pH and ionic strength compared to a bicarbonate solution, and only 5% of alkene conversion was observed after 24 h. In contrast to the simplicity of the homogeneous BAP procedure, the Payne procedure requires stirring and continuous addition of peroxide and base.
30. See Bach, R. D.; Glukhovtsev, M. N.; Gonzalez, C. J. Am. Chem. Soc: 1998, 120, 9902-9910 and references therein.
31. 3, and acetamide byproduct is observed.
32. Bolm, C.; Beckman, O.; Dabard, O. A. G. Angew. Chem., Int. Ed. 1999, 38, 907.
33. Dartt, C. B.; Davis, M. E. Ind. Eng. Chem. Res. 1994, 33, 2887.