Anaerobic Copper-Catalyzed Oxidation of Alcohols to Aldehydes and Ketones

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 20, 1997, Pages 2208-2210

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

^a UNIVERSITÉ CATHOLIQUE DE LOUVAIN   (Belgium)

^b ASTRAZENECA   (United Kingdom)

^c JEALOTT S HILL RESEARCH STATION   (United Kingdom)

Author keywords

Alcohols; Carbonyl compounds; Copper; Homogeneous catalysis; Oxidations

Indexed keywords

EID: 0030725046     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199722081     Document Type: Article

References (33)

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10. I. E. Markó, P. R. Giles, M. Tsukazaki, S. M. Brown, C. J. Urch, unpublished results.
11. 2, though in very low yields, has been reported previously: P. Capdevielle, P. Audebert, M. Maumy, Tetrahedron Lett. 1984, 25, 4397-4400.
12. 2, though in very low yields, has been reported previously: P. Capdevielle, P. Audebert, M. Maumy, Tetrahedron Lett. 1984, 25, 4397-4400.
13. 2, though in very low yields, has been reported previously: P. Capdevielle, P. Audebert, M. Maumy, Tetrahedron Lett. 1984, 25, 4397-4400.
14. 2, though in very low yields, has been reported previously: P. Capdevielle, P. Audebert, M. Maumy, Tetrahedron Lett. 1984, 25, 4397-4400.
15. 2, though in very low yields, has been reported previously: P. Capdevielle, P. Audebert, M. Maumy, Tetrahedron Lett. 1984, 25, 4397-4400.
16. For reviews on the formation, isolation and reactions of dinuclear copper(II) peroxides, see a) K. D. Karlin, Y. Gultneh, Prog. Inorg. Chem. 1987, 35, 219-327; b) A. D. Zuberbühler in Copper Coordination Chemistry: Biochemical and Inorganic Perspectives (Eds.: K. D. Karlin, J. Zubieta), Adenine Press, Guilderland, NY, 1983; c) A. M. Sakharov, I. P. Skibida, Kinet. Catal. Engl. Transl. 1988, 29, 96-102; d) Z. Tyleklar, R. R. Jacobson, N. Wei, N. N. Murthy, J. Zubieta, K. D. Karlin, J. Am. Chem. Soc. 1993, 115, 2677-2689; e) N. Kitajima, K. Fujisawa, C. Fujimoto, Y. Morooka, S. Hashimoto, T. Kitagawa, K. Toriumi, K. Tatsumi, A. Nakamura, ibid. 1992, 114, 1277-1291; f) S. Fox, A. Nanthakumar, M. Wikstrom, K. D. Karlin, N. J. Blackburn, ibid. 1996, 118, 24-34; g) E. I. Solomon, U. M. Sundaram, T. E. Machonkin, Chem. Rev. 1996, 96, 2563-2605.
17. For reviews on the formation, isolation and reactions of dinuclear copper(II) peroxides, see a) K. D. Karlin, Y. Gultneh, Prog. Inorg. Chem. 1987, 35, 219-327; b) A. D. Zuberbühler in Copper Coordination Chemistry: Biochemical and Inorganic Perspectives (Eds.: K. D. Karlin, J. Zubieta), Adenine Press, Guilderland, NY, 1983; c) A. M. Sakharov, I. P. Skibida, Kinet. Catal. Engl. Transl. 1988, 29, 96-102; d) Z. Tyleklar, R. R. Jacobson, N. Wei, N. N. Murthy, J. Zubieta, K. D. Karlin, J. Am. Chem. Soc. 1993, 115, 2677-2689; e) N. Kitajima, K. Fujisawa, C. Fujimoto, Y. Morooka, S. Hashimoto, T. Kitagawa, K. Toriumi, K. Tatsumi, A. Nakamura, ibid. 1992, 114, 1277-1291; f) S. Fox, A. Nanthakumar, M. Wikstrom, K. D. Karlin, N. J. Blackburn, ibid. 1996, 118, 24-34; g) E. I. Solomon, U. M. Sundaram, T. E. Machonkin, Chem. Rev. 1996, 96, 2563-2605.
18. For reviews on the formation, isolation and reactions of dinuclear copper(II) peroxides, see a) K. D. Karlin, Y. Gultneh, Prog. Inorg. Chem. 1987, 35, 219-327; b) A. D. Zuberbühler in Copper Coordination Chemistry: Biochemical and Inorganic Perspectives (Eds.: K. D. Karlin, J. Zubieta), Adenine Press, Guilderland, NY, 1983; c) A. M. Sakharov, I. P. Skibida, Kinet. Catal. Engl. Transl. 1988, 29, 96-102; d) Z. Tyleklar, R. R. Jacobson, N. Wei, N. N. Murthy, J. Zubieta, K. D. Karlin, J. Am. Chem. Soc. 1993, 115, 2677-2689; e) N. Kitajima, K. Fujisawa, C. Fujimoto, Y. Morooka, S. Hashimoto, T. Kitagawa, K. Toriumi, K. Tatsumi, A. Nakamura, ibid. 1992, 114, 1277-1291; f) S. Fox, A. Nanthakumar, M. Wikstrom, K. D. Karlin, N. J. Blackburn, ibid. 1996, 118, 24-34; g) E. I. Solomon, U. M. Sundaram, T. E. Machonkin, Chem. Rev. 1996, 96, 2563-2605.
19. For reviews on the formation, isolation and reactions of dinuclear copper(II) peroxides, see a) K. D. Karlin, Y. Gultneh, Prog. Inorg. Chem. 1987, 35, 219-327; b) A. D. Zuberbühler in Copper Coordination Chemistry: Biochemical and Inorganic Perspectives (Eds.: K. D. Karlin, J. Zubieta), Adenine Press, Guilderland, NY, 1983; c) A. M. Sakharov, I. P. Skibida, Kinet. Catal. Engl. Transl. 1988, 29, 96-102; d) Z. Tyleklar, R. R. Jacobson, N. Wei, N. N. Murthy, J. Zubieta, K. D. Karlin, J. Am. Chem. Soc. 1993, 115, 2677-2689; e) N. Kitajima, K. Fujisawa, C. Fujimoto, Y. Morooka, S. Hashimoto, T. Kitagawa, K. Toriumi, K. Tatsumi, A. Nakamura, ibid. 1992, 114, 1277-1291; f) S. Fox, A. Nanthakumar, M. Wikstrom, K. D. Karlin, N. J. Blackburn, ibid. 1996, 118, 24-34; g) E. I. Solomon, U. M. Sundaram, T. E. Machonkin, Chem. Rev. 1996, 96, 2563-2605.
20. For reviews on the formation, isolation and reactions of dinuclear copper(II) peroxides, see a) K. D. Karlin, Y. Gultneh, Prog. Inorg. Chem. 1987, 35, 219-327; b) A. D. Zuberbühler in Copper Coordination Chemistry: Biochemical and Inorganic Perspectives (Eds.: K. D. Karlin, J. Zubieta), Adenine Press, Guilderland, NY, 1983; c) A. M. Sakharov, I. P. Skibida, Kinet. Catal. Engl. Transl. 1988, 29, 96-102; d) Z. Tyleklar, R. R. Jacobson, N. Wei, N. N. Murthy, J. Zubieta, K. D. Karlin, J. Am. Chem. Soc. 1993, 115, 2677-2689; e) N. Kitajima, K. Fujisawa, C. Fujimoto, Y. Morooka, S. Hashimoto, T. Kitagawa, K. Toriumi, K. Tatsumi, A. Nakamura, ibid. 1992, 114, 1277-1291; f) S. Fox, A. Nanthakumar, M. Wikstrom, K. D. Karlin, N. J. Blackburn, ibid. 1996, 118, 24-34; g) E. I. Solomon, U. M. Sundaram, T. E. Machonkin, Chem. Rev. 1996, 96, 2563-2605.
21. For reviews on the formation, isolation and reactions of dinuclear copper(II) peroxides, see a) K. D. Karlin, Y. Gultneh, Prog. Inorg. Chem. 1987, 35, 219-327; b) A. D. Zuberbühler in Copper Coordination Chemistry: Biochemical and Inorganic Perspectives (Eds.: K. D. Karlin, J. Zubieta), Adenine Press, Guilderland, NY, 1983; c) A. M. Sakharov, I. P. Skibida, Kinet. Catal. Engl. Transl. 1988, 29, 96-102; d) Z. Tyleklar, R. R. Jacobson, N. Wei, N. N. Murthy, J. Zubieta, K. D. Karlin, J. Am. Chem. Soc. 1993, 115, 2677-2689; e) N. Kitajima, K. Fujisawa, C. Fujimoto, Y. Morooka, S. Hashimoto, T. Kitagawa, K. Toriumi, K. Tatsumi, A. Nakamura, ibid. 1992, 114, 1277-1291; f) S. Fox, A. Nanthakumar, M. Wikstrom, K. D. Karlin, N. J. Blackburn, ibid. 1996, 118, 24-34; g) E. I. Solomon, U. M. Sundaram, T. E. Machonkin, Chem. Rev. 1996, 96, 2563-2605.
22. For reviews on the formation, isolation and reactions of dinuclear copper(II) peroxides, see a) K. D. Karlin, Y. Gultneh, Prog. Inorg. Chem. 1987, 35, 219-327; b) A. D. Zuberbühler in Copper Coordination Chemistry: Biochemical and Inorganic Perspectives (Eds.: K. D. Karlin, J. Zubieta), Adenine Press, Guilderland, NY, 1983; c) A. M. Sakharov, I. P. Skibida, Kinet. Catal. Engl. Transl. 1988, 29, 96-102; d) Z. Tyleklar, R. R. Jacobson, N. Wei, N. N. Murthy, J. Zubieta, K. D. Karlin, J. Am. Chem. Soc. 1993, 115, 2677-2689; e) N. Kitajima, K. Fujisawa, C. Fujimoto, Y. Morooka, S. Hashimoto, T. Kitagawa, K. Toriumi, K. Tatsumi, A. Nakamura, ibid. 1992, 114, 1277-1291; f) S. Fox, A. Nanthakumar, M. Wikstrom, K. D. Karlin, N. J. Blackburn, ibid. 1996, 118, 24-34; g) E. I. Solomon, U. M. Sundaram, T. E. Machonkin, Chem. Rev. 1996, 96, 2563-2605.
23. 2 through the reaction mixture, a 60% conversion of p-chlorobenzylalcohol into p-chlorobenzaldehyde can be achieved. Allylic substrates gave much lower conversions (<30%) and aliphatic alcohols are virtually inert under these conditions. No reaction is observed with any of these substrates under anaerobic conditions, in the absence of the azo derivatives 3.
24. 2 through the reaction mixture containing 7 and alcohol 2 restored the catalytic activity, and good yields of aldehyde 6 were again obtained.
25. This new catalytic cycle, involving steps 2 and 6, is in some ways reminiscent of analogous oxidation shunts that take place in aerobic bacteria placed under anaerobic conditions.
26. The oxidation of alcohols with azodicarboxylates has been previously reported: F. Yoneda, K. Suzuki, Y. Nitta, J. Org. Chem. 1967, 32, 727-729. Control experiments were therefore performed to establish the need for copper salts in our anaerobic oxidation procedure. Thus, under our reaction conditions, no aldehyde or ketone could be detected in the absence of the CuCl·phen catalyst, even when phenanthroline was added as an activating base. Moreover, certain reactive alcohols were oxidized partially by CuCl·phen in the absence of the azo derivative 3, though only in moderate yields.
27. With most oxidants, α-hydroxyketones are oxidized with concomitant cleavage of the C-C bond: a) R. C. Larock, Comprehensive Organic Transformations, VCH, New York, 1989, pp. 604-615; b) R. A. Sheldon, J. K. Kochi, Metal-Catalyzed Oxidations of Organic Compounds, Academic Press, New York, 1981; c) G. Procter in Comprehensive Organic Synthesis, Vol. 7 (Eds.: B. M. Trost, I. Flemming, S. V. Ley), Pergamon, Oxford, 1991; d) W. S. Trahanovsky, Oxidation in Organic Chemistry, Part A-D, Academic Press, New York.
28. With most oxidants, α-hydroxyketones are oxidized with concomitant cleavage of the C-C bond: a) R. C. Larock, Comprehensive Organic Transformations, VCH, New York, 1989, pp. 604-615; b) R. A. Sheldon, J. K. Kochi, Metal-Catalyzed Oxidations of Organic Compounds, Academic Press, New York, 1981; c) G. Procter in Comprehensive Organic Synthesis, Vol. 7 (Eds.: B. M. Trost, I. Flemming, S. V. Ley), Pergamon, Oxford, 1991; d) W. S. Trahanovsky, Oxidation in Organic Chemistry, Part A-D, Academic Press, New York.
29. With most oxidants, α-hydroxyketones are oxidized with concomitant cleavage of the C-C bond: a) R. C. Larock, Comprehensive Organic Transformations, VCH, New York, 1989, pp. 604-615; b) R. A. Sheldon, J. K. Kochi, Metal-Catalyzed Oxidations of Organic Compounds, Academic Press, New York, 1981; c) G. Procter in Comprehensive Organic Synthesis, Vol. 7 (Eds.: B. M. Trost, I. Flemming, S. V. Ley), Pergamon, Oxford, 1991; d) W. S. Trahanovsky, Oxidation in Organic Chemistry, Part A-D, Academic Press, New York.
30. With most oxidants, α-hydroxyketones are oxidized with concomitant cleavage of the C-C bond: a) R. C. Larock, Comprehensive Organic Transformations, VCH, New York, 1989, pp. 604-615; b) R. A. Sheldon, J. K. Kochi, Metal-Catalyzed Oxidations of Organic Compounds, Academic Press, New York, 1981; c) G. Procter in Comprehensive Organic Synthesis, Vol. 7 (Eds.: B. M. Trost, I. Flemming, S. V. Ley), Pergamon, Oxford, 1991; d) W. S. Trahanovsky, Oxidation in Organic Chemistry, Part A-D, Academic Press, New York.
31. See for example M. T. Reetz, M. W. Drewes, A. Schmitz, Angew. Chem. 1987, 99, 1186-1188; Angew. Chem. Int. Ed. Engl. 1987, 26, 1141-1143.
32. See for example M. T. Reetz, M. W. Drewes, A. Schmitz, Angew. Chem. 1987, 99, 1186-1188; Angew. Chem. Int. Ed. Engl. 1987, 26, 1141-1143.
33. This difference appears to be due to competitive autooxidation of the aldehyde to the corresponding carboxylic acid by oxygen at high conversions of the alcohol. See also ref. [9b].