Efficient Oxidative Scission of Alkenes or Alkynes with Heterogeneous Ruthenium Zirconia Catalyst

루테늄 지르코니아 불균일 촉매를 이용한 알켄 또는 알킨의 효과적인 산화절단반응

  • Irshad, Mobina (Department Chemical Engineering, Kangwon National University) ;
  • Choi, Bong Gill (Department Chemical Engineering, Kangwon National University) ;
  • Kang, Onyu (Department Chemical Engineering, Kangwon National University) ;
  • Hong, Seok Bok (Department Chemical Engineering, Kangwon National University) ;
  • Hwang, Sung Yeon (Korea Research Institute of Chemical Technology) ;
  • Heo, Young Min (SKC Advanced Technology R&D Center) ;
  • Kim, Jung Won (Department Chemical Engineering, Kangwon National University)
  • Received : 2016.11.14
  • Accepted : 2016.11.28
  • Published : 2016.12.10


The efficiency of a heterogeneous ruthenium zirconia catalyst ($Ru(OH)_x/ZrO_2$) was demonstrated to the selective oxidative transformation of alkenes or alkynes. The scissions of C-C double bonds to aldehydes and triple bonds to diketones or carboxylic acids were carried out with (diacetoxyiodo)benzene as an oxidant under dichloromethane (5 mL)/water (0.5 mL) solvent system at $30^{\circ}C$ for wide range of substrates. The $Ru(OH)_x/ZrO_2$composite showed higher catalytic activity and selectivity than other ruthenium-based homogeneous or heterogeneous catalysts for the scission reaction. The catalyst exhibited a high mechanical stability, and no leaching of the metal was observed during the reaction. These features ensured the reusability of the catalyst for several times for the oxidative cleavage of unsaturated hydrocarbons.


Supported by : Kangwon National University


  1. P. Daw, R. Petakamsetty, A. Sarbajna, S. Laha, R. Ramapanicker, and J. K. Bera, A highly efficient catalyst for selective oxidative scission of olefins to aldehydes: Abnormal-NHC-Ru(II) complex in oxidation chemistry, J. Am. Chem. Soc., 136, 13987-13990 (2014).
  2. D. G. Lee and T. Chen, Comprehensive organic synthesis. In: P. Knochel and G. A. Molander (eds.). Cleavage Reactions, 541-591, Elsevier, Oxford, UK (1991).
  3. Y. Nishiyama, Y. Nakagawa, and N. Mizuno, High turnover numbers for the catalytic selective epoxidation of alkenes with 1 atm of molecular oxygen, Angew. Chem. Int. Ed., 40, 3639-3641 (2001).<3639::AID-ANIE3639>3.0.CO;2-0
  4. I. V. Soares, E. G. Vieira, N. L. D. Filho, A. C. Bastos, N. C. da Silva, E. F. Garcia, and L. J. A. Lima, Adsorption of heavy metal ions and epoxidation catalysis using a new polyhedral oligomeric silsesquioxane, Chem. Eng. J., 218, 405-414 (2013).
  5. G. B. Dong, P. Teo, Z. K. Wickens, and R. H. Grubbs, Primary alcohols from terminal olefins: Formal anti-Markovnikov hydration via triple relay catalysis, Science, 333, 1609-1612 (2011).
  6. V. V. Namboodiri, R. S. Varma, E. S. Demessie, and U. R Pillai, Selective oxidation of styrene to acetophenone in the presence of ionic liquids, Green Chem., 4, 170-173 (2002).
  7. S. Chen, Z. Liu, E. Shi, L. Chen, W. Wei, H. Li, Y. Cheng, and X. Wan, Ruthenium catalyzed oxidation of alkenes at room temperature: A practical and concise approach to r-diketones, Org. Lett., 13, 2274-2277 (2011).
  8. M. R. Maurya, A. Kumar, and J. C. Pessoa, Vanadium complexes immobilized on solid supports and their use as catalysts for oxidation and functionalization of alkanes and alkenes, Coord. Chem. Rev., 255, 2315-2344 (2011).
  9. W. Jiang, J. D. Gorden, and C. R. Goldsmith, A homogeneous gallium (III) compound selectively catalyzes the epoxidation of alkenes, Inorg. Chem., 51, 2725-2727 (2012).
  10. P. Shringarpure and A. Patel, Cobalt (II) exchanged supported 12-tungstophosphoric acid: Synthesis, characterization and non-solvent liquid phase aerobic oxidation of alkenes, J. Mol. Catal. A, 321, 22-26 (2010).
  11. M. Moghadam, V. Mirkhani, S. Angestaninejad, I. Mohammadpoor-Baltork, and M. M. Javadi, Molybdenum schiff base-polyoxometalate hybrid compound: A heterogeneous catalyst for alkene epoxidation with tert-BuOOH, Polyhedron, 29, 648-654 (2010).
  12. M. Vafaeezadeh and M. M. Hashemi, Dual catalytic function of the task-specific ionic liquid: Green oxidation of cyclohexene to adipic acid using 30% $H_2O_2$, Chem. Eng. J., 221, 254-257 (2013).
  13. B. Weiner, A. Baeza, T. Jerphagnon, and B. L. Feringa, Aldehyde selective wacker oxidations of phthalimide protected allylic amines: A new catalytic route to ${\beta}3$-amino acids, J. Am. Chem. Soc., 131, 9473-9474 (2009).
  14. S. Baskaran, S. J. Das, and S. Chandrasekaran, Heterogeneous permanganate oxidations: an improved procedure for the direct conversion of olefins to ${\alpha}$-diketones/${\alpha}$-hydroxy ketones, J. Org. Chem., 54, 5182-5184 (1989).
  15. B. Travis, R. S. Narayan, and B. Borhan, Osmium tetroxide-promoted catalytic oxidative cleavage of olefins: An organometallic ozonolysis, J. Am. Chem. Soc., 124, 3824-3825 (2002).
  16. D. C. Whitehead, B. R. Travis, and B. Borhan, The $OsO_4$-mediated oxidative cleavage of olefins catalyzed by alternative osmium sources, Tetrahedron Lett., 47, 3797-3800 (2006).
  17. O. Hiroshi, O. Kazuhiro, and B. Shinji, Use of the composite material $RuO_2/BaTi_4O_9$ as an environmentally benign solid catalyst for the oxidative cleavage of olefins, Synlett., 3201-3205 (2007).
  18. M. O. F. Goulart, A. G. Cioletti, J. D. de Souza Filho, C. A. de Simone, E. E. Castellano, F. S. Emery, K. C. G. de Moura, M. C. F. R. Pintod, and A. V. Pinto, Unexpected oxidation of a substituted benzo[a]phenazine: Oxidative cleavage of a double bond and formation of a macrolactone, Tetrahedron Lett., 44, 3581-3585 (2003).
  19. J. H. Noh, R. Patala, and R. Meijboom, Catalytic evaluation of dendrimer and reverse microemulsion template Pd and Pt nanoparticles for the selective oxidation of styrene using TBHP, Appl. Catal. A, 514, 253-266 (2016).
  20. D. Xing, B. Guan, G. Cai, Z. Fang, L. Yang, and Z. Shi, Gold(I)-catalyzed oxidative cleavage of a C-C double bond in water, Org. Lett., 8, 693-696 (2006).
  21. Y.-H. Kim, S.-Y. Hwang, J. W. Kim, and Y.-S. Lee, Zriconia supported ruthenium catalyst for efficient aerobic oxidation of alcohols to aldehydes, Ind. Chem. Eng. Res., 53, 12548-12552 (2014).
  22. N. M. Neisius and B. Plietke, Diastereoselective Ru-catalyzed cross-metathesis-dihydroxylation sequence: An efficient approach toward enantiomerically enriched syn-diols, J. Org. Chem., 73, 3218-3227 (2008).
  23. Z. Hong, L. Liu, M. Sugiyama, Y. Fu, and C. H. Wong, Concise synthesis of iminocyclitols via petasis-type aminocyclization, J. Am. Chem. Soc., 131, 8352-8353 (2009).
  24. A. Gao, F. Yang, J. Li, and Y. Wu, Pd/Cu-catalyzed oxidation of alkynes into 1,2-diketones using DMSO as the oxidant, Tetrahedron, 68, 4950-4954 (2012).
  25. Y. Xu and X. Wan, Ruthenium-catalyzed oxidation of alkynes to 1,2-diketones under room temperature and one-pot synthesis of quinoxalines, Tetrahedron Lett., 54, 642-645 (2013).