Simple and Practical Aerobic Oxidation of Alcohols Catalyzed by a (μ-Oxo)tetraruthenium Cluster
Teruyuki Kondo, Yu Kimura, Takashi Kanda, Daisuke Takagi, Kenji Wada, Akio Toshimitsu
DOI: 10.4236/gsc.2011.14023   PDF   HTML     6,199 Downloads   12,630 Views   Citations


A (μ-oxo)tetraruthenium cluster showed high catalytic activity for a simple and practical aerobic oxidation of alcohols to aldehydes and ketones under 1 atm of O2 or air. After the reaction, this cluster catalyst was re- covered from the reaction mixture, and we believe that this (μ-oxo)tetraruthenium cluster acts as an active catalytic species throughout the reaction.

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T. Kondo, Y. Kimura, T. Kanda, D. Takagi, K. Wada and A. Toshimitsu, "Simple and Practical Aerobic Oxidation of Alcohols Catalyzed by a (μ-Oxo)tetraruthenium Cluster," Green and Sustainable Chemistry, Vol. 1 No. 4, 2011, pp. 149-154. doi: 10.4236/gsc.2011.14023.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] I. W. C. E. Arends and R. A. Sheldon, “Modern Oxidation of Alcohols Using Environmentally Benign Oxidants,” In: J.-E. Bäckvall, Ed., Modern Oxidation Methods, Wiley-VCH, Weinheim, 2004, pp. 83-118.
[2] I. W. C. E. Arends and R. A. Sheldon, “Modern Oxidation of Alcohols Using Environmentally Benign Oxidants,” In: J.-E. Bäckvall, Ed., Modern Oxidation Methods, 2nd Edition, Wiley-VCH, Weinheim, 2010, pp. 147- 185. doi:10.1002/9783527632039.ch5
[3] M. B. Smith and J. March, “March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure,” 6th Edition, John Wiley & Sons, New Jersey, 2007, pp. 1703- 1786.
[4] P. T. Anastas, “Green Catalysis,” Wiley-VCH, Weinheim, 2009.
[5] M. Kitamura and R. Noyori, “Hydrogenation and Transfer Hydrogenation,” In: S. -I. Murahashi, Ed., Ruthenium in Organic Synthesis, Wiley-VCH, Weinheim, 2004, pp. 3-52.
[6] S. -I. Murahashi and N. Komiya, “Oxidation Reactions,” In: S. -I. Murahashi, Ed., Ruthenium in Organic Synthesis, Wiley-VCH, Weinheim, 2004, pp. 53-93. doi:10.1002/3527603832
[7] I. W. C. E. Arends, T. Kodama, and R. A. Sheldon, “Oxi- dation Using Ruthenium Catalysts,” In: C. Bruneau and P. H. Dixneuf, Eds., Ruthenium Catalysts and Fine Chemistry, Springer, Berlin, 2004, pp. 277-320.
[8] W. S. Trahanovsky, “Oxidation in Organic Chemistry,” Academic Press, Cleveland, 1973.
[9] Y. Tsuji, T. Ohta, T. Ido, H. Minbu and Y. Watanabe, “Ruthenium-Catalyzed Oxidation of Alcohols and Catechols Using t-Butyl Hydroperoxide,” Journal of Organo- metallic Chemistry, Vol. 270, No. 3, 1984, pp. 333-341. doi:10.1016/0022-328X(84)80381-2
[10] S.-I. Murahashi and T. Naota, “Ruthenium-Catalyzed O- xidations for Selective Syntheses of Ketones and Acyl Cyanides. Selective Acylation of Amino Compounds with Acyl Cyanides,” Synthesis, Vol. 50, No. 4, 1993, pp. 433-440. doi:10.1055/s-1993-25877
[11] K. B. Sharpless, K. Akashi and K. Oshima, “Ruthenium- Catalyzed Oxidation of Alcohols to Aldehydes and Ketones by Amine-N-Oxides,” Tetrahedron Letters, Vol. 17, No. 29, 1976, pp. 2503-2506. doi:10.1016/S0040-4039(00)78130-5
[12] P. Müller and J. Gody, “Catalyzed Oxidation of Alcohols and Aldehydes with Iodosylbenzene,” Tetrahedron Letters, Vol. 22, No. 25, 1981, pp. 2361-2364. doi:10.1016/S0040-4039(01)82906-3
[13] Y. Yamamoto, H. Suzuki and Y. Moro-oka, “Ruthenium- Catalyzed Oxidation of Alcohols with Sodium Bromate,” Tetrahedron Letters, Vol. 26, No. 17, 1985, pp. 2107- 2108. doi:10.1016/S0040-4039(00)94791-9
[14] S. Kanemoto, H. Tomioka, K. Oshima and H. Nozaki, “Cerium or Ruthenium-Catalysed Oxidation of Alcohols to Carbonyl Compounds by means of Sodium Bromate,” Bulletin of the Chemical Society of Japan, Vol. 59, No. 1, 1986, pp. 105-108. doi:10.1246/bcsj.59.105
[15] J.-E. Bäckvall, R. L. Chowdhury and U. Karisson, “Ruthenium-Catalyzed Aerobic Oxidation of Alcohols via Multistep Electron Transfer,” Journal of the Chemical Society, Chemical Communications, No. 7, 1991, pp. 473-475. doi:10.1039/C39910000473
[16] C. Csjernyik, A. H. éll, L. Fadini, B. Pugin and J.-E. Bäckvall, “Efficient Ruthenium-Catalyzed Aerobic Oxidation of Alcohols Using a Biomimetic Coupled Catalytic System,” Journal of Organic Chemistry, Vol. 67, No. 5, 2002, pp. 1657-1662. doi:10.1021/jo0163750
[17] E. V. Johnston, E. A. Karlsson, L.-H. Tran, B. Åkermark and J.-E. Bäckvall, “Efficient Aerobic Ruthenium-Catal- yzed Oxidation of Secondary Alcohols by the use of a Hybrid Electron Transfer Catalyst,” European Journal of Organic Chemistry, No. 10, 2010, pp. 1971-1976. doi:10.1002/ejoc.201000033
[18] F. Shi, M. K. Tse and M. Beller, “A Novel Environmentally Benign Method for the Selective Oxidation of Alcohols to Aldehydes and Ketones,” Chemistry, An Asian Journal, Vol. 2, No. 3, 2007, pp. 411-415. doi:10.1002/asia.200600383
[19] A. Dijksman, A. Marino-González, A. M. i Payeras, I. W. C. E. Arends and R. A. Sheldon, “Efficient and Selective Aerobic Oxidation of Alcohols into Aldehydes and Ketones Using Ruthenium/TEMPO as the Catalytic System,” Journal of the American Chemical Society, Vol. 123, No. 28, 2001, pp. 6826-6833. doi:10.1021/ja0103804
[20] C. Bilgrien, S. Davis and R. S. Drago, “The Selective Oxidation of Primary Alcohols to Aldehydes by O2 Employing a Trinuclear Ruthenium Carboxylate Catalyst,” Journal of the American Chemical Society, Vol. 109, No. 12, 1987, pp. 3786-3787. doi:10.1021/ja00246a049
[21] I. E. Markó, P. R. Giles, M. Tsukazaki, I. Chellé-Regnaut, C. J. Urch and S. M. Brown, “Efficient, Aerobic, Ruthenium-Catalyzed Oxidation of Alcohols into Aldehydes and Ketones,” Journal of the American Chemical Society, Vol. 119, No. 51, 1997, 12661-12662. doi:10.1021/ja973227b
[22] N. Zotova, K. Hellgardt, G. H. Kelsall, A. S. Jessiman and K. K. Hill, “Catalysis in Flow: The Practical and Selective Aerobic Oxidation of Alcohols to Aldehydes and Ketones,” Green Chemistry, Vol. 12, No. 12, 2010, 2157- 2163. doi:10.1039/c0gc00493f
[23] T. Mitsudo, Y. Ura and T. Kondo, “Chemistry of Ru (η6- 1,3,5-cyclooctatriene)(η2-dimethyl fumarate)2,” Chemical Record, Vol. 6, No. 3, 2006, pp. 107-116. doi:10.1002/tcr.20076
[24] T. Mitsudo, Y. Ura and T. Kondo, “Chemistry of a Novel Zerovalent Ruthenium π-Acidic Alkene Complex, Ru(η6- 1,3,5-cyclooctatriene)(η2-dimethyl fumarate)2,” Proceedings of the Japan Academy, Series B, Vol. 83, No. 3, 2007, pp. 65-76. doi:10.2183/pjab.83.65
[25] T. Kondo, “On Inventing Catalytic Reactions via Ruthena- or Rhodacyclic Intermediates for Atom Economy,” Synlett, No. 5, 2008, pp. 629-644. doi:10.1055/s-2008-1042807
[26] T. Kondo, “New Catalytic Performances of Ruthenium and Rhodium Complexes Directed toward Organic Synthesis with High Atom Efficiency,” Bulletin of the Che- mical Society of Japan, Vol. 84, No. 5, 2011, pp. 441-458. doi:10.1246/bcsj.20110019
[27] T. Kondo, F. Tsunawaki, T. Suzuki, Y. Ura, K. Wada, S. Yamaguchi, H. Masuda, K. Yoza, M. Shiro and T. Mit- sudo, “Synthesis and Characterization of a Novel (μ3- Oxo)tetraruthenium Cluster,” Journal of Organometallic Chemistry, Vol. 692, No. 1-3, 2007, pp. 530-535. doi:10.1016/j.jorganchem.2006.08.062
[28] T. Mitsudo, T. Suzuki, S.-W. Zhang, D. Imai, K.i Fujita, T. Manabe, M. Shiotsuki, Y. Watanabe, K. Wada and T. Kondo, “Novel Ruthenium Complex-Catalyzed Dimerization of 2,5-Norbornadiene to Pentacyclo[6.6.02,6. 03,13. 010,14]-tetradeca-4,11-diene Involving Carbon-Carbon Bond Clea- vage,” Journal of the American Chemical Society, Vol. 121, No. 9, 1999, pp. 1839-1850. doi:10.1021/ja9835741
[29] M. S. Thompson and T. J. Meyer, “Mechanisms of Oxidation of 2-Propanol by Polypyridyl Complexes of Ruthenium(III) and Ruthenium(IV),” Journal of the American Chemical Society, Vol. 104, No. 15, 1982, pp. 4106- 4115. doi:10.1021/ja00379a011
[30] C. S. Yi, T. N. Zeczycki and I. A. Guzei, “Highly Cooperative Tetrametallic Ruthenium-μ-Oxo-μ-Hydroxo Ca- talyst for the Alcohol Oxidation Reaction,” Organome- tallics, Vol. 25, No. 4, 2006, pp. 1047-1051. doi:10.1021/om0510674
[31] A. M. Khenkin, L. J. W. Shimon and R. Neumann, Preparation and Characterization of New Ruthenium and Os- mium Containing Polyoxo-metalates, [M(DMSO)3M7O24]4– (M = Ru(II), Os(II)), and Their Use as Catalysts for the Aerobic Oxidation of Alcohols,” Inorganic Chemistry, Vol. 42, No. 10, 2003, pp. 3331-3339. doi:10.1021/ic026003p
[32] F. Nikaidou, H. Ushiyama, K. Yamaguchi, K. Yamashita and N. Mizuno, “Theoretical and Experimental Studies on Reaction Mechanism for Aerobic Alcohol Oxidation by Supported Ruthenium Hydroxide Catalysts,” Journal of Physical Chemistry C, Vol. 114, No. 24, 2010, pp. 10873-10880. doi:10.1021/jp101692j
[33] A. B. Pangborn, M. A. Giardello, R. H. Grubbs, R. K. Rosen and F. J. Timmers, “Safe and Convenient Procedure for Solvent Purification,” Organometallics, Vol. 15, No. 5, 1996, pp. 1518-1520. doi:10.1021/om9503712
[34] C. Pouchert, “Aldrich Library of 13C and 1H FT-NMR Spectra,” John Wiley & Sons, Chichester, 1993.

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