Catalytic synthesis of aldehydes and ketones under mild conditions using tempo/oxone

Organic Letters

Volumn 2, Issue 8, 2000, Pages 1173-1175

  Bolm, Carsten ^a   Magnus, Angelika S ^a   Hildebrand, Jens P ^a  

^a RWTH AACHEN UNIVERSITY   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0041402599     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol005792g     Document Type: Article

References (38)

1. (a) Sheldon, R. A.; Kochi, J. K. Metal-Catalyzed Oxidations of Organic Compounds; Academic Press: New York 1984.
2. (b) Hudlicky, M. Oxidations in Organic Chemistry; ACS Monograph 186; 1990.
3. (a) For an excellent overview, see: Ley, S. V.; Norman, J.; Griffith, W. P.; Marsden, S. P. Synthesis 1994, 639-666.
4. (b) See also: Markó, I. E.; Giles, P. R.; Tsukazaki, M.; Chélle-Regnaut, I.; Urch, C. J.; Brown, S. M. J. Am. Chem. Soc. 1997, 119, 12661-12662 and references therein.
5. (a) Markó, I. E.; Gautier, A.; Giles, P. R.; Chélle-Regnaut, I.; Tsukazaki, M.; Urch, C. J.; Brown, S. M. J. Org. Chem. 1998, 63, 7576-7577.
6. (b) Markó, I. E.; Giles, P. R.; Tsukazaki, M.; Chélle-Regnaut, I.; Gautier, A.; Brown, S. M.; Urch, C. J. J. Org. Chem. 1999, 64, 2433-2439.
7. (c) Semmelhack, M. F.; Schmidt, C. R.; Cortés, D. A.; Chou, C. S. J. Am. Chem. Soc. 1984, 106, 3374-3376.
8. For a palladium-based catalyst-system with molecular oxygen as oxidant, see: Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750-6755 and references therein.
9. Zhao, M.; Li, J.; Song, Z.; Desmond, R.; Tschaen, D. M.; Grabowski, E. J. J.; Reider, P. J. Tetrahedron Lett. 1998, 39, 5323-5326.
10. (a) Sato, K.; Aoki, M.; Takagi, J.; Noyori, R. J. Am. Chem. Soc. 1997, 119, 12386-12387.
11. (b) Sato, K.; Aoki, M.; Noyori, R. Science 1998, 281, 1646-1647.
12. For overviews and leading early contributions, see: (a) de Nooy, A. E. J.; Besemer, A. C.; Bekkum, H. V. Synthesis 1996, 1153-1174.
13. (b) Bobbit, J. M.; Flores, M. C. L. Heterocycles 1988, 27, 509-533.
14. (c) Anelli, P. L.; Biffi, C.; Montanari, F.; Quici, S. J. Org. Chem. 1987, 52, 2559-2562.
15. (d) Miyazawa, T.; Endo, T.; Shiihashi, S.; Okawara, M. J. Org. Chem. 1985, 50, 1332-1334.
16. Selected references on various oxidations: (a) Bolm, C.; Schlingloff, G.; Weickhardt, K. Angew. Chem., Int. Ed. Engl. 1994, 33, 1848-1849.
17. (b) Bolm, C.; Bienewald, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 2640-2642.
18. (c) Bolm, C.; Kadereit, D.; Valacchi, M. Synlett 1997, 687-688.
19. (d) Bolm, C.; Maischak, A.; Gerlach, A. Chem. Commun. 1997, 2353-2354.
20. (e) Bolm, C. Med. Chem. Res. 1999, 19, 348-356.
21. Bolm, C.; Fey, T. Chem. Commun. 1999, 1795-1796.
22. In addition, the use of aqueous bleach often leads to chlorinated byproducts which lower the yield and can make product isolation problematic.
23. 4.
24. This result is not due to overoxidation of the aldehydes to their corresponding carboxylic acids.
25. See reference 7a. For a recent report on the oxidation of primary alcohols to the corresponding carboxylic acids using TEMPO, see: Zhao, M.; Li, J.; Mano, E.; Song, Z.; Tschaen, D. M.; Grabowski, E. J. J.; Reider, P. J. J. Org. Chem. 1999, 64, 2564-2566.
26. For selected examples on oxidations of secondary alcohols to ketones, see: (a) Cella, J. A.; Kelley; J. A.; Kenehan, E. F. J. Org. Chem. 1975, 40, 1860-1862.
27. (b) Cella, J. A.; McGrath, J. P.; Kelley, J. A.; ElSoukkary, O.; Hilpert, L. J. Org. Chem. 1977, 42, 2077-2080.
28. (c) Inokuchi, T.; Matsumoto, S.; Nishiyama, T.; Torii, S. J. Org. Chem. 1990, 55, 462-466.
29. (d) Banwell, M. G. Bridges, V. S.; Dupuche, J. R.; Richards, S. L., Walter, J. M. J. Org. Chem. 1994, 59, 6338-6343.
30. (e) Drauz, K.; Kottenhahn, M.; Stingel, K. US Patent 5631385.
31. (f) De Mico, A.; Margarita, R.; Parlanti, L.; Vescovi, A.; Pincatelli, G. J. Org. Chem. 1997, 62, 6974-6977.
32. (g) Dijksman, A.; Arends, I. W. C. E.; Sheldon, R. A. Chem. Commun. 1999, 1591-1592 and references therein.
33. Rychnovsky, S. D.; Vaidjanathan, R. J. Org. Chem. 1999, 64, 310-312.
34. Chloride ion proved also successful probably due to the formation of the corresponding hypochlorous acid.
35. The presence of acids inhibited the catalysis.
36. Control experiments revealed that in the absence of TEMPO aldehydes and ketones were also formed though in low yield. Without ammonium salt no oxidation was observed.
37. 4NBr (4 mol %, 0.04 mmol) in 5 mL of the indicated solvent is added TEMPO (1 mol %, 0.01 mmol, 0.1 M solution of the indicated solvent) and Oxone (2.2 equiv, 2.2 mmol). The mixture is then stirred for 12 h at room temperature, and the reaction is monitored by TLC. After the rection is complete, the solvent is removed under reduced pressure, and the remaining solid is purified by column chromatography (silica gel, hexanes/ethyl acetate: 10/1).
38. Sabitha, G.; Syamala, M.; Jadav, J. S. Org. Lett. 1999, 1, 1701-1703.