Enantioselective epoxidation of styrene using in-situ generated dimethyldioxirane and dimeric homochiral Mn(III)-Schiff base complex catalyst

Brayan David Verdugo-Torres, Jairo Antonio Cubillos-Lobo, Hugo Alfonso Rojas-Sarmiento


The enantioselective epoxidation of styrene using in-situ generated dimethyldioxirane (DMD) and dimeric homochiral Mn(III)-Schiff base catalyst 1 has been explored. The parameters evaluated were olefin/oxidant molar ration, catalyst loading, reaction temperature and presence of nitrogen coordinating co-catalysts. Conversions of more than 99% and enantiomeric excess 66% were obtained. The selectivity is complete towards styrene oxide using 2 mol% catalyst loading, 1.36 mmol KHSO5 in 8 ml of water, absence of co-catalyst and 17 °C as reaction temperature. Furthermore, the catalyst could be recycled up to three times with slightly decrease of catalytic activity due mainly to the physical loss of the catalyst during the recovery step and at a lesser extent as a consequence of its oxidative degradation.


Enantioselective epoxidation; Styrene; Dimethyldioxirane; Dimeric catalyst, catalysts reusability

Full Text:



Y. Chen and et al., “Reusable chiral salen Mn(III) complexes with phase transfer capability efficiently catalyze the asymmetric epoxidation of unfunctionalized olefins with NaClO,” Applied Catalysis A: General, vol. 495, pp. 106–115, Feb. 2015.

A. Lattanzi, Asymmetric Epoxidations of ,-Unsaturated Carbonyl Compounds. Wiley-Blackwell, 2010, ch. 9, pp. 351–391.

V. Caprio and J. Williams, “Epoxidation,” in Catalysis in Asymmetric Synthesis. United Kingdom: Wiley-Blackwell, 2009, pp. 88–90.

Q. H. Xia, H. Q. Ge, C. P. Ye, Z. M. Liu, and K. X. Su, “Advances in homogeneous and Heterogeneous Catalytic Asymmetric Epoxidation,” Chemical Reviews, vol. 105, no. 5, pp. 1603–1662, 2005.

Z. Wang, “Jacobsen-Katsuki Epoxidation,” in Comprehensive Organic Name Reactions and Reagents, Z. Wang, Ed. USA: Wiley, 2009, p. 1534.

H. Adolfsson, “Product class 2: Epoxides (Oxiranes),” in Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 37: Ethers, C. J. Forsyth, Ed. Stuttgart, Germany: Georg Thieme Verlag, 2014, p. 251.

R. I. Kureshy and et al., “Enantioselective epoxidation of nonfunctionalized alkenes catalyzed by recyclable new homochiral dimeric mn(III) salen complexes,” Aerosp. and Electron. Syst., vol. 224, no. 2, pp. 229–235, Jun. 2004.

J. Cubillos, S. Vásquez, and C. M. de Correa, “Salen manganese (III) complexes as catalysts for R-(+)-limonene oxidation,” Applied Catalysis A: General, vol. 373, no. 1-2, pp. 57–65, Jan. 2010.

K. C. Gupta, A. K. Sutar, and C. C. Lin, “Polymer-supported Schiff base complexes in oxidation reactions,” Coordination Chemistry Reviews, vol. 253, no. 13–14, pp. 1926–1946, Jul. 2009.

A. S. Amarasekara, I. McNeal, J. Murillo, D. Green, and A. Jennings, “A simple one-pot synthesis of Jacobson–Katsuki type chiral Mn(III)– salen catalyst immobilized in silica by sol–gel process and applications in asymmetric epoxidation of alkenes,” Catalysis Communications, vol. 9, no. 14, pp. 2437–2440, Aug. 2008.

X. Tang, Y. Tang, G. Xu, S. Wei, and Y. Sun, “Highly enantioselective epoxidation of styrene and α-methylstyrene catalyzed by new doubly-immobilized chiral (salen)mn(III) catalysts,” Catalysis Communications, vol. 10, no. 3, pp. 317–320, Dec. 2008.

W. Ren and X. Fu, “Chiral mn (iii) salen complexes covalently bonded on zirconium oligostyrenylphosphonate-phosphates as catalysts for enantioselective epoxidation of nonfunctionalized alkenes,” Journal of Molecular Catalysis A: Chemical, vol. 312, no. 1-2, pp. 40–47, Oct. 2009.

X. Tu, X. Fu, X. Hu, and Y. Li, “Chiral salen mn(III) immobilized on sulfoalkyl modified zsp-ippa as an effective catalyst for asymmetric epoxidation of unfunctionalized olefins,” Inorganic Chemistry Communications, vol. 13, no. 3, pp. 404–407, Ma.r 2010.

R. I. .Kureshy and et al., “Encapsulation of a chiral MnIII(salen) complex in ordered mesoporous silicas: an approach towards heterogenizing asymmetric epoxidation catalysts for non-functionalized alkenes,” Tetrahedron: Asymmetry, vol. 16, no. 21, pp. 3562–3569, Oct. 2005.

——, “Dicationic chiral Mn(III) salen complex exchanged in the interlayers of montmorillonite clay: a heterogeneous enantioselective catalyst for epoxidation of nonfunctionalized alkenes,” Journal of Catalysis, vol. 221, no. 1, pp. 234–240, Jan. 2004.

S. Tangestaninejad, M. Moghadam, V. M. I. M. Baltorkand, and M. S. Saeedi, “Efficient epoxidation of alkenes with sodium periodate catalyzed by reusable manganese(iii) salophen supported on multi-wall carbon nanotubes,” Applied Catalysis A: General, vol. 381, no. 1-2, pp. 233–241, Jun. 2010.

R. Tan, D. Yin, N. Yu, H. Zhao, and D. Yin, “Easily recyclable polymeric ionic liquid-functionalized chiral salen Mn(III) complex for enantioselective epoxidation of styrene,” Journal of Catalysis, vol. 263, no. 2, pp. 284–291, Apr. 2009.

Y. Chen and et al., “Reusable chiral salen Mn(III) complexes with phase transfer capability efficiently catalyze the asymmetric epoxidation of unfunctionalized olefins with naclo,” Applied Catalysis A: General, vol. 491, no. 5, pp. 106–115, Feb. 2015.

J. M. Fraile, J. I. García, J. A. Mayoral, and E. Pires, “Heterogenization on inorganic supports: Methods and applications,” in Heterogenized Homogeneous Catalysts for Fine Chemicals Production: Materials and Processes. Dordrecht, Holanda Meridional: Springer Netherlands, 2010, pp. 65–119.

R. I. Kureshy, N. H. Khan, S. H. R. Abdi, and R. V. Jasra, “New approaches to develop recyclable catalyst for the synthesis of chiral epoxides,” in Catalysis Research at the Cutting Edge, L. P. Bevy, Ed. New York, NY: Nova Science Publishers, 2005, p. 126.

S. M. Coman, G. Poncelet, and V. I. Pârvulescu, “Asymmetric Catalysis by Heterogeneous Catalysts,” in Surface and Nanomolecular Catalysis, R. Richards, Ed. Boca Raton, Florida: CRC Press, 2006, p. 495.

O. Deutschmann, H. Knözinger, K. Kochloefl, and T. Turek, Heterogeneous Catalysis and Solid Catalysts. American Cancer Society, 2009.

R. I. Kureshy and et al., “Enantioselective epoxidation of nonfunctionalised alkenes catalysed by dimeric homochiral mn(iii) salen complex using oxone as oxidant,” Journal of Molecular Catalysis A: Chemical, vol. 203, no. 1-2, pp. 69–73, Sep. 2003.

R. Ji, K. Yu, L. L. Lou, and S. Liu, “Reactivity comparison of epoxidation of unfunctionalized olefins with different oxidants catalyzed by mesoporous silica supported unsymmetric chiral Mn (III) salen complexes in heterogeneous condition,” Journal of Molecular Catalysis A: Chemical, vol. 378, pp. 7–16, Nov. 2013.

F. P.Ballistrerio and et al, “Enantioselective epoxidations of alkenes catalyzed by (salen)Mn(III) in aqueous surfactant systems,” Tetrahedron, vol. 64, no. 44, pp. 10 239–10 243, Oct. 2008.

C. Baleizão and H. Garcia, “Chiral salen complexes: An Overview to Recoverable and Reusable Homogeneous and Heterogeneous Catalysts,” Chemical Reviews, vol. 106, no. 9, pp. 3987–4043, 2006.

J. Huang, Y. Iuo, and J. Cai, “Enantioselective epoxidation of unfunctionalized olefins by jacobsen’s catalyst immobilized on aminomodified ZnPS-PVPA,” Chinese Journal of Catalysis, vol. 37, no. 9, pp. 1539–1548, Sep. 2016.

J. Huang, L. Yuan, J. Cai, and D. Qi, “Effect of linkers on the performance of znps-brppas supported chiral Mn (III) salen for the epoxidation of unfunctionalized olefins,” Synthetic Metals, vol. 115, pp. 104–109, May. 2016.

P. Pietikäineno, “Convenient asymmetric (salen)Mn(III)-catalyzed epoxidation of unfunctionalized alkenes with hydrogen peroxide using carboxylate salt cocatalysts,” Tetrahedron, vol. 54, no. 17, pp. 4319–4326, Apr. 1998.

T. Yamada, Kiyomi Imagawa, Takushi Nagata, and Teruaki Mukaiyama, “Aerobic Enantioselective Epoxidation of Unfunctionalized Olefins Catalyzed by Optically Active Salen-Manganese (III) Complexes,” Bulletin of the Chemical Society of Japan, vol. 67, no. 8, pp. 2248–2256, Aug. 1994.

A. Saeed and et al., “Recent resurgence toward the oxidation of heteroatoms using dimethyldioxirane as an exquisite oxidant,” Synthetic Communications, vol. 47, no. 9, pp. 835–852, 2017.

W. Adam and et al., “Enantioselective epoxidation of 2,2-dimethyl- 2H-chromenes by dimethyldioxirane and jacobsen’s Mn(III)salen catalysts,” Tetrahedron Letters, vol. 36, no. 21, pp. 3669–3672, May. 1995.

——, “Enantioselective epoxidation of isoflavones by jacobsen’s Mn(IIi)salen catalysts and dimethyldioxirane oxygen-atom source,” Tetrahedron: Asymmetry, vol. 9, no. 7, pp. 1121–1124, Apr. 1998.

J. Cubillos and W. Hölderich, “Jacobsen’s catalyst anchored on Al-MCM-41 and NH2 group modified Si-MCM-41 as heterogeneous enantioselective epoxidation catalyst using in situ generated dimethyldioxirane as oxidant,” Revista Facultad de Ingeniería Universidad de Antioquia, no. 41, pp. 31–47, Sep. 2017.

K. B. M.Janssen and et al., “A dimeric form of jacobsen’s catalyst for improved retention in a polydimethylsiloxane membrane,” Tetrahedron: Asymmetry, vol. 8, no. 20, pp. 3481–3487, Oct. 1997.

M. Barwiolek, E. Szlyk, A. Surdykowski, and A. Wojtczak, “New nickel(II) and copper(II) complexes with unsymmetrical schiff bases derived from (1R,2R)(−)cyclohexanediamine and the application of cu(II) complexes for hybrid thin layers deposition,” Dalton Trans., vol. 42, pp. 11 476–11 487, 2013.

R. I. Kureshy, N. H. Khan, S. H. R. Abdi, S. T. Patel, and R. V. Jasrav, “Enantioselective epoxidation of non-functionalised alkenes using a urea–hydrogen peroxide oxidant and a dimeric homochiral Mn(III)- schiff base complex catalyst,” Tetrahedron: Asymmetry, vol. 12, no. 3, pp. 433–437, Mar. 2001.

F. Rojo. (2016) Tablas de Espectroscopía Infrarroja. [Online]. Available: http://depa.fquim.unam.mx/amyd/archivero/TablasIR_34338. pdf

B. M. Dioos and P. A. Jacobs, “Impregnation of dimeric CrIII(salen) on silica and its application in epoxide asymmetric ring opening reactions,” Applied Catalysis A: General, vol. 282, no. 1-2, pp. 181–188, Mar. 2005.

R. Luo and et al., “Stable chiral salen Mn(III) complexes with built-in phase-transfer capability for the asymmetric epoxidation of unfunctionalized olefins using NaOCl as an oxidant,” Journal of catalysis, vol. 287, pp. 170–177, Mar. 2012.

T. Katsuki, Asymmetric Oxidations and Related Reactions: Asymmetric Epoxidation of Unfunctionalized Olefins and Related Reactions. Wiley- Blackwell, 2005, pp. 287–325.

DOI: https://doi.org/10.17533/udea.redin.n89a10 Abstract : 461 PDF : 138

Article Metrics

Metrics Loading ...

Metrics powered by PLOS ALM

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.

Esta publicación hace parte del Sistema de Revistas de la Universidad de Antioquia
¿Quieres aprender a usar el Open Journal system? Ingresa al Curso virtual
Este sistema es administrado por el Programa Integración de Tecnologías a la Docencia
Universidad de Antioquia
Powered by Public Knowledge Project