Copper-catalyzed oxidation of alcohols to aldehydes and ketones: An efficient, aerobic alternative

Science

Volumn 274, Issue 5295, 1996, Pages 2044-2046

  Markó, István E ^a   Giles, Paul R ^a   Tsukazaki, Masao ^a   Brown, Stephen M ^b   Urch, Chistopher J ^c  

^a UNIVERSITÉ CATHOLIQUE DE LOUVAIN   (Belgium)

^b ASTRAZENECA   (United Kingdom)

^c JEALOTT S HILL RESEARCH STATION   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL; ALDEHYDE; COPPER; KETONE;

AEROBIC METABOLISM; ALCOHOL OXIDATION; ARTICLE; KETOGENESIS; OXIDATION REDUCTION REACTION; PRIORITY JOURNAL;

EID: 0030460515     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.274.5295.2044     Document Type: Article

References (36)

1. For general reviews on oxidation reactions, see R. C. Larock, Comprehensive Organic Transformations (VCH Publishers, New York, 1989), pp. 604-615; R. A. Sheldon and J. K. Kochi, Metal-Catalysed Oxidations of Organic Compounds (Academic Press, New York, 1931); W. P. Griffith and J. M. Joliffe, Dioxygen Activation and Homogeneous Catalytic Oxidation, L. L. Simandi, Ed. (Elsevier, Amsterdam, 1991); G. Procter, Comprehensive Organic Synthesis, S. V. Ley, Ed, (Pergamon, Oxford, 1991), vol. 7.
2. For general reviews on oxidation reactions, see R. C. Larock, Comprehensive Organic Transformations (VCH Publishers, New York, 1989), pp. 604-615; R. A. Sheldon and J. K. Kochi, Metal-Catalysed Oxidations of Organic Compounds (Academic Press, New York, 1931); W. P. Griffith and J. M. Joliffe, Dioxygen Activation and Homogeneous Catalytic Oxidation, L. L. Simandi, Ed. (Elsevier, Amsterdam, 1991); G. Procter, Comprehensive Organic Synthesis, S. V. Ley, Ed, (Pergamon, Oxford, 1991), vol. 7.
3. For general reviews on oxidation reactions, see R. C. Larock, Comprehensive Organic Transformations (VCH Publishers, New York, 1989), pp. 604-615; R. A. Sheldon and J. K. Kochi, Metal-Catalysed Oxidations of Organic Compounds (Academic Press, New York, 1931); W. P. Griffith and J. M. Joliffe, Dioxygen Activation and Homogeneous Catalytic Oxidation, L. L. Simandi, Ed. (Elsevier, Amsterdam, 1991); G. Procter, Comprehensive Organic Synthesis, S. V. Ley, Ed, (Pergamon, Oxford, 1991), vol. 7.
4. For general reviews on oxidation reactions, see R. C. Larock, Comprehensive Organic Transformations (VCH Publishers, New York, 1989), pp. 604-615; R. A. Sheldon and J. K. Kochi, Metal-Catalysed Oxidations of Organic Compounds (Academic Press, New York, 1931); W. P. Griffith and J. M. Joliffe, Dioxygen Activation and Homogeneous Catalytic Oxidation, L. L. Simandi, Ed. (Elsevier, Amsterdam, 1991); G. Procter, Comprehensive Organic Synthesis, S. V. Ley, Ed, (Pergamon, Oxford, 1991), vol. 7.
5. For catalytic oxidations, see, for example, S. V. Ley, J. Norman, W. P. Griffith, S. P. Marsden, Synthesis (1994), p. 639; S. I. Murahashi, T. Naota, Y. Oda, N. Hirai, Synlett. (1995), p. 733; K. Krohn, I. Vinke, H. Adam, J. Org. Chem. 61, 1467 (1996), and references therein.
6. For catalytic oxidations, see, for example, S. V. Ley, J. Norman, W. P. Griffith, S. P. Marsden, Synthesis (1994), p. 639; S. I. Murahashi, T. Naota, Y. Oda, N. Hirai, Synlett. (1995), p. 733; K. Krohn, I. Vinke, H. Adam, J. Org. Chem. 61, 1467 (1996), and references therein.
7. For catalytic oxidations, see, for example, S. V. Ley, J. Norman, W. P. Griffith, S. P. Marsden, Synthesis (1994), p. 639; S. I. Murahashi, T. Naota, Y. Oda, N. Hirai, Synlett. (1995), p. 733; K. Krohn, I. Vinke, H. Adam, J. Org. Chem. 61, 1467 (1996), and references therein.
8. For other catalytic aerobic oxidations, see, for example, S.-I. Murahashi, T. Naota, J. Hirai, J. Org. Chem. 58, 7318 (1993); T. Inokuchi, K. Nakagawa, S. Torii, Tetrahedron Lett. 36, 3223 (1995); T. Iwahama, S. Sakaguchi, Y. Nishiyama, Y. Ishii, ibid., p. 6923, and references therein.
9. For other catalytic aerobic oxidations, see, for example, S.-I. Murahashi, T. Naota, J. Hirai, J. Org. Chem. 58, 7318 (1993); T. Inokuchi, K. Nakagawa, S. Torii, Tetrahedron Lett. 36, 3223 (1995); T. Iwahama, S. Sakaguchi, Y. Nishiyama, Y. Ishii, ibid., p. 6923, and references therein.
10. For other catalytic aerobic oxidations, see, for example, S.-I. Murahashi, T. Naota, J. Hirai, J. Org. Chem. 58, 7318 (1993); T. Inokuchi, K. Nakagawa, S. Torii, Tetrahedron Lett. 36, 3223 (1995); T. Iwahama, S. Sakaguchi, Y. Nishiyama, Y. Ishii, ibid., p. 6923, and references therein.
11. 2 is used in the presence of at least a stoichiometric amount of a reactive aldehyde such as pivalaldehyde. The active oxidizing species is probably the peracid or the metal-peracyl derivative. Under these conditions, 1 equivalent of acid is always formed as a by-product.
12. C. Jallabert and H. Rivière, Tetrahedron Lett. (1977), p. 1215; C. Jallabert, C. Lapinte, H. Rivière, J. Mol. Calai. 7, 127 (1980); C. Jallabert and H. Rivière, Tetrahedron 36, 1191 (1980); C. Jallabert, C. Lapinte, H. Rivière, J. Mol. Catal. 14, 75 (1982).
13. C. Jallabert and H. Rivière, Tetrahedron Lett. (1977), p. 1215; C. Jallabert, C. Lapinte, H. Rivière, J. Mol. Calai. 7, 127 (1980); C. Jallabert and H. Rivière, Tetrahedron 36, 1191 (1980); C. Jallabert, C. Lapinte, H. Rivière, J. Mol. Catal. 14, 75 (1982).
14. C. Jallabert and H. Rivière, Tetrahedron Lett. (1977), p. 1215; C. Jallabert, C. Lapinte, H. Rivière, J. Mol. Calai. 7, 127 (1980); C. Jallabert and H. Rivière, Tetrahedron 36, 1191 (1980); C. Jallabert, C. Lapinte, H. Rivière, J. Mol. Catal. 14, 75 (1982).
15. C. Jallabert and H. Rivière, Tetrahedron Lett. (1977), p. 1215; C. Jallabert, C. Lapinte, H. Rivière, J. Mol. Calai. 7, 127 (1980); C. Jallabert and H. Rivière, Tetrahedron 36, 1191 (1980); C. Jallabert, C. Lapinte, H. Rivière, J. Mol. Catal. 14, 75 (1982).
16. For other pertinent studies on aerobic oxidation of alcohols with copper complexes, see, for example, P. Capdevielle, D. Sparfel, J. Baranne-Lafont, N. K. Cuong, M. Maumy, J. Chem. Res. (S) 1993, 10 (1993), and references therain; M. Munakata, S. Nishibayashi, H. Sakamoto, J. Chem. Soc. Chem. Commun. (1980), p. 219; S. Bhaduri and N. Y. Sapre, J. Chem. Soc. Dalton Trans. (1981), p. 2585; M. F. Semmelhack, C. R. Schmid, D. A. Cortes, C. S. Chon, J. Am. Chem. Soc. 106, 3374 (1984).
17. For other pertinent studies on aerobic oxidation of alcohols with copper complexes, see, for example, P. Capdevielle, D. Sparfel, J. Baranne-Lafont, N. K. Cuong, M. Maumy, J. Chem. Res. (S) 1993, 10 (1993), and references therain; M. Munakata, S. Nishibayashi, H. Sakamoto, J. Chem. Soc. Chem. Commun. (1980), p. 219; S. Bhaduri and N. Y. Sapre, J. Chem. Soc. Dalton Trans. (1981), p. 2585; M. F. Semmelhack, C. R. Schmid, D. A. Cortes, C. S. Chon, J. Am. Chem. Soc. 106, 3374 (1984).
18. For other pertinent studies on aerobic oxidation of alcohols with copper complexes, see, for example, P. Capdevielle, D. Sparfel, J. Baranne-Lafont, N. K. Cuong, M. Maumy, J. Chem. Res. (S) 1993, 10 (1993), and references therain; M. Munakata, S. Nishibayashi, H. Sakamoto, J. Chem. Soc. Chem. Commun. (1980), p. 219; S. Bhaduri and N. Y. Sapre, J. Chem. Soc. Dalton Trans. (1981), p. 2585; M. F. Semmelhack, C. R. Schmid, D. A. Cortes, C. S. Chon, J. Am. Chem. Soc. 106, 3374 (1984).
19. For other pertinent studies on aerobic oxidation of alcohols with copper complexes, see, for example, P. Capdevielle, D. Sparfel, J. Baranne-Lafont, N. K. Cuong, M. Maumy, J. Chem. Res. (S) 1993, 10 (1993), and references therain; M. Munakata, S. Nishibayashi, H. Sakamoto, J. Chem. Soc. Chem. Commun. (1980), p. 219; S. Bhaduri and N. Y. Sapre, J. Chem. Soc. Dalton Trans. (1981), p. 2585; M. F. Semmelhack, C. R. Schmid, D. A. Cortes, C. S. Chon, J. Am. Chem. Soc. 106, 3374 (1984).
20. For oxidation of alcohols into acids with copper complexes, see V. P. Tetyakov, G. P. Zimtseva, E. S. Ruddkov, A. V. Bogdanov, React. Kinet. Catal. Lett. 19, 263 (1982); A. M. Sakharov and I. P. Skibida, J. Mol. Catal. 48,157 (1988); L. Feldberg and Y. Sasson, J. Chem. Soc. Chem. Commun. (1994), p. 1807.
21. For oxidation of alcohols into acids with copper complexes, see V. P. Tetyakov, G. P. Zimtseva, E. S. Ruddkov, A. V. Bogdanov, React. Kinet. Catal. Lett. 19, 263 (1982); A. M. Sakharov and I. P. Skibida, J. Mol. Catal. 48,157 (1988); L. Feldberg and Y. Sasson, J. Chem. Soc. Chem. Commun. (1994), p. 1807.
22. For oxidation of alcohols into acids with copper complexes, see V. P. Tetyakov, G. P. Zimtseva, E. S. Ruddkov, A. V. Bogdanov, React. Kinet. Catal. Lett. 19, 263 (1982); A. M. Sakharov and I. P. Skibida, J. Mol. Catal. 48,157 (1988); L. Feldberg and Y. Sasson, J. Chem. Soc. Chem. Commun. (1994), p. 1807.
23. Stoichiometric amounts of substituted azo-compounds have been used to oxidize magnesium alkoxides to the corresponding carbonyl compounds; see K. Narasaka, A. Morikawa, K. Saigo, T. Mukaiyama, Bull. Chem. Soc. Jpn. 50, 2773 (1977). The decomposition mechanism of hydrazines in the presence of copper-complexes has been reported; see H. Erlenmeyer, C. Fliert, H. Sigel, J. Am. Chem. Soc. 91, 1065 (1969); Y. Zhong and P. K. Lim, ibid. 111, 8398 (1989).
24. Stoichiometric amounts of substituted azo-compounds have been used to oxidize magnesium alkoxides to the corresponding carbonyl compounds; see K. Narasaka, A. Morikawa, K. Saigo, T. Mukaiyama, Bull. Chem. Soc. Jpn. 50, 2773 (1977). The decomposition mechanism of hydrazines in the presence of copper-complexes has been reported; see H. Erlenmeyer, C. Fliert, H. Sigel, J. Am. Chem. Soc. 91, 1065 (1969); Y. Zhong and P. K. Lim, ibid. 111, 8398 (1989).
25. Stoichiometric amounts of substituted azo-compounds have been used to oxidize magnesium alkoxides to the corresponding carbonyl compounds; see K. Narasaka, A. Morikawa, K. Saigo, T. Mukaiyama, Bull. Chem. Soc. Jpn. 50, 2773 (1977). The decomposition mechanism of hydrazines in the presence of copper-complexes has been reported; see H. Erlenmeyer, C. Fliert, H. Sigel, J. Am. Chem. Soc. 91, 1065 (1969); Y. Zhong and P. K. Lim, ibid. 111, 8398 (1989).
26. -, and p-xylene or trimethylbenzene were tested. None proved as efficient as toluene. The reason for the enhanced competency of toluene over other solvents is not yet understood.
27. In view of the low cost of the copper(I) chloride and Phen ligand used, we typically use 5 mol % of the complex. This amount also ensures rapid oxidation of the alcohol substrates.
28. 2.
29. 2, smooth transformation into the corresponding carbonyl compound ensues, thus indicating the heterogeneous nature of the active oxidant.
30. 2, though in very low yields, has been reported previously: P. Capdevielle, P. Audebert, M. Maumy, Tetrahedron Lett. 25, 4397 (1984).
31. 2O can also be used. A catalytic amount of base is still required to initiate the reaction.
32. 2. In the presence of oxygen, smooth oxidation of an alcohol takes place.
33. For excellent reviews on the formation, isolation, and reactions of dinuclear copper (II) peroxides, see K. D. Karlin and Y. Gultneh, Prog, Inorg. Chem. 35, 219 (1987); A. D. Zuberbühler, in Copper Coordination Chemistry: Biochemical and Inorganic Perspectives, K. D. Karlin and J. Zubieta, Eds. (Adenine, Guilderland, NY, 1983), p. 237.
34. For excellent reviews on the formation, isolation, and reactions of dinuclear copper (II) peroxides, see K. D. Karlin and Y. Gultneh, Prog, Inorg. Chem. 35, 219 (1987); A. D. Zuberbühler, in Copper Coordination Chemistry: Biochemical and Inorganic Perspectives, K. D. Karlin and J. Zubieta, Eds. (Adenine, Guilderland, NY, 1983), p. 237.
35. c 191.3, 141.5, 135.4, 131.5, and 130.0.
36. Dedicated to the memory of Zdenek Janousek. Financial support of this work was provided by Zeneca Limited, through the Zeneca Strategic Research Fund. I.E.M. is grateful to Zeneca for receiving the Zeneca Fellowship (1994-1997).