EFFICIENT, ECOLOGICALLY BENIGN, AEROBIC OXIDATION OF ALCOHOLS

Advances in Inorganic Chemistry

Volumn 56, Issue , 2004, Pages 211-240

  MARKÓ, ISTVÁN E ^a   GILES, PAUL R ^a   TSUKAZAKI, MASAO ^a   CHELLÉ REGNAUT, ISABELLE ^a   GAUTIER, ARNAUD ^a   DUMEUNIER, RAPHAEL ^a   PHILIPPART, FREDDI ^a   DODA, KANAE ^a   MUTONKOLE, JEAN LUC ^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

[No Author keywords available]

Indexed keywords

EID: 27644586813     PISSN: 08988838     EISSN: None     Source Type: Book Series    
DOI: 10.1016/S0898-8838(04)56007-5     Document Type: Review

References (93)

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36. (c) Markó, I. E.; Tsukazaki, M.; Giles, P. R.; Brown, S. M.; Urch, C. J. Angew. Chem. Int. Ed., Engl. 1997, 36, 2208;
37. (d) Markó, I. E.; Giles, P. R.; Tsukazaki, M.; Brown, S. M.; Urch, C. J. "Transition Metals for Organic Synthesis"; chapter 2.12, Vol. 2; Eds. Beller, M.; Bolm, C.; 1998, p. 350;
38. (e) Markó, I. E.; Gautier, A.; Chellé-Regnaut, I.; Giles, P. R.; Tsukazaki, M.; Urch, C. J.; Brown, S. M. J. Org. Chem 1998, 63, 7576;
39. (f) Marko, I. E.; Gautier, A.; Mutonkole, J.-L.; Dumeunier, R.; Ates, A.; Urch, C. J.; Brown, S. M. J. Organomet. Chem. 2001, 624, 344;
40. For an independent report of the aerobic TPAP catalysed oxidation of alcohols see: Lenz, R.; Ley, S. V. J. Chem. Soc., Perkin I 1997, 3291.
41. For excellent reviews on the formation isolation and reactions of dinuclear copper (II) peroxides see: (a) Karlin, K. D.; Gultneh, Y. Progress in Inorganic Chemistry 1987, 35, 219-327;
42. (b) Zuberbühler, A. D. "Copper Coordination Chemistry: Biochemical and Inorganic Perspectives"; Eds. Karlin, K. D.; Zubieta, J.; Adenine: Guilderland, New York, 1983;
43. (c) Sakharov, A. M.; Skibida, I. P. Kinetics and Catalysis 1988, 29, 96-102;
44. (d) Tyleklar, Z.; Jacobson, R. R.; Wei, N.; Murthy, N. N.; Zubieta, J.; Karlin, K. D. J. Am. Chem. Soc. 1993, 115, 2677-2689;
45. (e) Kitajima, N.; Fujisawa, K.; Fujimoto, C.; Moro-oka, Y.; Hashimoto, S.; Kitagawa, T.; Toriumi, K.; Tatsumi, K.; Nakamura, A. ibid 1992, 114, 1277-1291;
46. (f) Fox, S.; Nanthakumar, A.; Wikstrom, M.; Karlin, K. D.; Blackburn, N. J. ibid. 1996, 118, 24-34;
47. (g) Solomon, E. I.; Sundaram, U. M.; Machonkin, T. E. Chem. Rev. 1996, 96, 2563-2605.
48. (a) Jallabert, C.; Rivière, H. Tetrahedron Lett. 1977, 1215;
49. (b) Jallabert, C.; Lapinte, C.; Rivière, H. J. Mol. Catal 1980, 7, 127;
50. (c) Jallabert, C.; Rivière, H. Tetrahedron 1980, 36, 1191;
51. (d) Jallabert, C.; Lapinte, C.; Rivière, H. J. Mol. Catal. 1982, 14, 75;
52. For other pertinent studies on aerobic oxidation of alcohols using copper complexes see for example: (a) Capdevielle, P.; Sparfel, D.; Baranne-Lafont, J.; Cuong, N. K.; Maumy, M. J. Chem. Research, (S) 1993, 10 and references cited therein;
53. (b) Munakata, M.; Nishibayashi, S.; Sakamoto, H. J. Chem. Soc., Chem. Commun. 1980, 219;
54. (c) Bhaduri, S.; Sapre, N. Y. J. Chem. Soc., Dalton Trans. 1981, 2585;
55. (d) Semmelhack, M. F.; Schmid, C. R.; Cortes, D. A.; Chon, C. S. J. Am. Chem. Soc 1984, 106, 3374.
56. See for example Ref. (8a).
57. t appears to act as an efficient base in the catalytic oxidation process. Its use is however limited at present to the oxidation of secondary alcohols (Markó, I. E.; Gautier, A.; Chellé-Régnaut, I.; Mutonkole K. Unpublished results).
58. Solomon, R. G.; Kochi, J. K. . J. Am. Chem. Soc 1973, 95, 3300.
59. The use of air instead of oxygen results in a slower reaction rate. The oxidation can be increased by passing the air through a porous glass frit which creates microbubbles. Under these conditions, the speed of the catalytic oxidation of alcohols using air matches the one employing oxygen.
60. 2 have been reported in the literature. See for example: Capdevielle, P.; Audebert, P.; Maumy, M. Tetrahedron Lett. 1984, 25, 4397-4400.
61. Stoichiometric amounts of substituted azo-compounds have been used to oxidize magnesium alkoxides to the corresponding carbonyl compounds: Narasaka, K.; Morikawa, A.; Saigo, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1977, 50, 2773;
62. The decomposition mechanism of hydrazines in the presence of copper-complexes has been reported: (a) Erlenmeyer, H.; Flierl, C.; Sigel, H. J. Am. Chem. Soc. 1969, 91, 1065;
63. (b) Zhong, Y.; Lim, P. K. J. Am. Chem. Soc 1989, 111, 8398.
64. Alcohols containing nitrogen heterocycles are also smoothly oxidized to the corresponding carbonyl compounds. These heterocycles include pyridine, imidazole and triazole derivatives.
65. 2 through the reaction mixture containing 13 and alcohol 1 restored the catalytic activity and good yields of aldehyde 2 were again obtained.
66. (a) Sustmann, R.; Müller, W.; Mignani, S.; Merényi, R.; Janousek, Z.; Viehe, H. G. New. J. Chem. 1989, 13, 557;
67. (b) De Boeck, B.; Janousek, Z.; Viehe, H. G. Tetrahedron 1995, 51, 13239-13246.
68. For general reviews on Oppenauer-type oxidations see: (a) de Graauw, C. F.; Peters, J. A.; Vandekkum, H.; Huskens, J. Synthesis 1994, 1007-1017;
69. (b) Djerassi, C. Org. React. (N.Y.) 1951, 6, 207-212;
70. (c) Krohn, K.; Knauer, B.; Kupke, J.; Seebach, D.; Beck, A. K.; Hayakawa, M. Synthesis 1996, 1341-1344.
71. The use of stoichiometric amounts of dipiperidinyl azodicarboxamide to oxidize magnesium alkoxides to the corresponding carbonyl compounds has been described: Narasaka, K.; Morikawa, A.; Saigo, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn 1977, 50, 2773. No reaction is observed under our catalytic anaerobic conditions if DBAD is replaced by the azodicarboxamide derivative..
72. Another argument against the oxo-transfer mechanism in our catalytic aerobic oxidation protocol is the lack of formation of sulfoxides from sulfides, N-oxydes from amines and phosphine oxydes from phosphines. Alkenes also proved to be inert towards oxidation; no epoxide formation could be detected under our reaction conditions.
73. The oxidation of alcohols using azodicarboxylates has been previously reported (Yoneda, F.; Suzuki, K.; Nitta, Y. J. Org. Chem 1967, 32, 727-729). Control experiments were therefore performed to establish the need for copper salts in our oxidation procedure. Thus under our reaction conditions no aldehyde or ketone could be detected in the absence of the CuCl·Phen catalyst even if phenanthroline was added as an activating base. Moreover, certain reactive alcohols were oxidized partially by CuCl·Phen in the absence of the azo-derivative 19, though only in moderate yields. These control experiments thus clearly establish the key-role of the copper ion in these oxidations.
74. The oxidation reactions were monitored by GC (Permabond SE-52-DF-0.25; 25 m x 0.25 mm ID) using tetradecane as the internal standard.
75. 2 and isobutene.
76. t, toluene, 80-90°C) afforded 2-undecanone in almost quantitative yields. However, this system appears, so far, to be limited to secondary alcohol oxidations.
77. For a discussion of the possible mechanism of this reaction, see: Markó, I. E.; Tsukazaki, M.; Giles, P. R.; Brown, S. M.; Urch, C. J. Angew. Chem. Int. Ed., Engl. 1997, 36, 2208.
78. 2Cl, DMF, and MeCN).
79. 2/aldehyde protocol: Yamada, T.; Imagawa, K.; Nagata, T.; Mukaiyama, T. Chem. Lett. 1992, 11, 2231.
80. A small amount of racemisation was observed during the oxidation of Boc-prolinol.
81. 5 (Naumenko, N. V.; Mukhin, N. N.; Aleskovikii, V. B. Zh. Prikl. Khim (Leningrad) 1969, 42, 2522). Furthermore fluorobenzene possesses unusual solvent property parameters and is more polar than toluene. (Table Presented) Like most aromatic solvents fluorobenzene is highly flammable (Fp=-12°C). It is irritant to the skin and can cause serious damage to the eyes. It is only weakly toxic by inhalation (rat; LC50=27 mg/l) and even less by ingestion (rat; LC50=4000 mg/l). On large-scale experiments it can be easily recycled by drying and distillation
82. It is possible that the greater polarity of flurorobenzene, which can lead to a higher concentration of soluble base, might be responsible in part for the improved yields and rate of reaction observed in this medium. Moreover, the amount of oxygen dissolved in boiling fluorobenzene might be greater than in toluene, leading to a more efficient reoxidation of the active copper species. In this regard, it is noteworthy that ¢nely divided oxygen or air bubbles (obtained by passing the gas through a glass frit) results in enhanced reaction rate.
83. tBuOK in the absence of added alcohol.
84. R (S)-enantiomer, 43.6 min).
85. (a) Karlin, K. D.; Gultneh, Y. Progr. Inorg. Chem 1987, 35, 219;
86. (b) Sakharov, A. M.; Skibida, I. P. Kinet. Catal 1988, 29, 96;
87. (c) Kitajima, N.; Fujisawa, K.; Fujimoto, C.; Moro-oka, Y.; Hashimoto, S.; Kitagawa, T.; Toriumi, K.; Tatsumi, K.; Nakamura, A. J. Am. Chem. Soc. 1992, 114, 1277;
88. (d) Solomon, E. I.; Sundaram, U. M.; Machonkin, T. E. Chem. Rev. 1996, 96, 2563.
89. Whereas quantitative conversion of 23 into 24 occurred in the absence and presence of 7 mol% of NMI, the oxidation of 23 proceeded more slowly in the presence of this additive. The coordination of NMI to copper results in a slower exchange with the excess DBAD and hence, in a longer reaction time.
90. Studies performed on the anaerobic version of this catalytic system revealed that aliphatic primary alcohols were oxidized with the same efficiency as all the other classes of alcohols, thus ruling out complexes A, B, and E as the culprit for the decomposition pathway. Whilst we could not experimentally disgard complex D, coordination of an alcohol to D should involve the participation of a pentacoordinated copper species. Whilst these are not uncommon, their formation requires a higher activation energy than the coordination to C.
91. 2 is unable to displace the alkoxide ligand from the copper complex G.
92. We have previously demonstrated that G was not a competent catalyst in the aerobic oxidation protocol when R=alkyl.
93. Markó, I. E.; Tsukazaki, M.; Giles, P. R.; Brown, S. M.; Urch, C. J. Angew. Chem. Int. Ed., Engl. 1997, 36, 2208.