Abstract
Hydrogen peroxide constitutes a potentially green and environmentally-friendly oxidant because it releases only water as by-product. Thus, much efforts have been put into the research for ideal conditions for its use in oxidation reactions. This chapter focuses on the recent applications of hydrogen peroxide in epoxidation reactions catalyzed by transition metal catalysts, illustrating both homogeneous and heterogeneous catalysis. An overview of the recent findings in asymmetric catalytic epoxidations is also given.
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References
R. A. Sheldon, Consider the environmental quotient, CHEMTECH 3, 38-47 (1994).
J. -E. Bäckvall, 2004, Modern Oxidation Methods, WILEY-VCH, Weinheim.
B. M. Trost, The atom economy: a search for synthetic efficiency, Science 254, 1471-1477 (1991).
a) J. T. Groves, R. Quinn, Aerobic epoxidation of olefins with ruthenium porphyrin catalysts, J. Am. Chem. Soc. 107, 5790-5792 (1985). b) C. Döbler, G. Mehltretter, M. Beller, Atom-efficient oxidation of alkenes with molecular oxygen: synthesis of diols, Angew. Chem. Int. Ed. 38, 3026-3028 (1999).
J. M. Campos-Martin, G. Blanco-Brieva, J. L. G. Fierro, Hydrogen peroxide synthesis, an outlook beyond the anthraquinone process, Angew. Chem. Int. Ed. 45, 6962-6984 (2006).
C. Venturello, R. D’Aloisio, J. C. J. Bart, M. Ricci, A new peroxotungsten heteropoly anion with special oxidizing properties: synthesis and structure of tetrahexylammonium tetra(diperoxotungsto)phosphate(3-), J. Mol. Catal. 32, 107-110 (1985).
C. Venturello, E. Alneri, M. Ricci, A new, effective catalytic system for epoxidation of olefins by hydrogen peroxide under phase-transfer conditions, J. Org. Chem. 48, 3831-3833 (1983).
K. Kamata, K. Yonehara, Y. Sumida, K. Yamaguchi, S. Hikichi, N. Mizuno, Efficient epoxidation of olefins with ≥99% selectivity and use of hydrogen peroxide, Science 300, 964-966 (2003).
K. Sato, M. Aoki, M. Ogawa, T. Hashimoto, R. Noyori, A practical method for epoxidation of terminal olefins with 30% hydrogen peroxide under halide-free conditions, J. Org. Chem. 61, 8310-8311 (1996).
M. Taramasso, G. Perego, B. Notari US Pat. 1983, 4.410.501.
M. G. Clerici, P. Ingallina, Epoxidation of lower olefins with hydrogen peroxide and titanium silicalite, J. Catal. 140 (1), 71-83 (1993).
M. G. Clerici and P. Ingallina in: Green Chemistry, designing Chemistry for the Environment, edited by P. T. Anastas, T. C. Williamson (American Chemical Society, Washington DC, 1996), pp. 59-68.
X. Zuwei, Z. Ning, S. Yu, L. Kunlan, Reaction-controlled phase-transfer catalysis for propylene epoxidation to propylene oxide, Science 292, 1139-1141 (2001).
C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli, J. S. Beck, Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism, Nature 359, 710-712 (1992).
P. T. Tanev, M. Chibwe, T. J. Pinnavaia, Titanium-containing mesoporous molecular sieves for catalytic oxidation of aromatic compounds, Nature 368, 321-323 (1994).
T. Maschmeyer, F. Rey, G. Sankar, J. M. Thomas, Heterogenous catalysts obtained by grafting metallocene complexes onto mesoporous silica, Nature 378, 159-162 (1995).
W. A. Herrmann, F. E. Kühn, Organorhenium oxides, Acc. Chem. Res. 30, 169-180 (1997).
C. C. Romao, F. E. Kühn, W. A. Herrmann, Rhenium(VII) oxo and imido complexes: synthesis, structures and applications, Chem. Rev. 97, 3197-3246 (1997).
S. Owens, J. Arias, M. M. Abu-Omar, Rhenium oxo complexes in catalytic oxidations, Catal. Today 55, 317-363 (2000).
F. E. Kühn, W. A. Herrmann, Methyltrioxorhenium, Chemtracts 14, 59-83 (2001).
G. Soldaini, Methyltrioxorhenium (MTO), Synlett 1849-1850 (2004).
W. A. Herrmann, R. W. Fischer, D. W. Marz, Multiple bonding between main group elements and transition metals. 100. Part 2. Methyltrioxorhenium as catalyst for olefin oxidation, Angew. Chem. Int. Ed. Engl. 30, 1638-1641 (1991).
I. R. Beattie, P. J. Jones, Methyltrioxorhenium. An air-stable compound containing a carbon-rhenium bond. Inorg. Chem. 18, 2318-2319 (1979).
W. M. Adam, C. M. Mitchell, Methyltrioxorhenium(VII)-catalyzed epoxidation of alkenes with the urea/hydrogen peroxide adduct, Angew. Chem. Int. Ed. Engl. 35, 533-535 (1996).
J. Rudolph, K. L. Reddy, J. P. Chiang, K. B. Sharpless, Highly efficient epoxidation of olefins using aqueous H2O2 and catalytic methyltrioxorhenium/pyridine: pyridinemediated ligand acceleration, J. Am. Chem. Soc. 119, 6189-6190 (1997).
C. Copéret, H. Adolfsson, K. B. Sharpless, A simple and efficient method for epoxidation of terminal alkenes, Chem. Commun. 1565-1566 (1997).
H. Adolfsson, C. Copéret, J. P. Chiang, A. K. Yudin, Efficient epoxidation of alkenes with aqueous hydrogen peroxide catalyzed by methyltrioxorhenium and 3-cyanopyridine, J. Org. Chem. 65, 8651-8658 (2000).
W. A. Herrmann, R. M. Kratzer, H. Ding, W. R. Thiel, H. Gras, Methyltrioxorhenium/ pyrazole-a highly efficient catalyst in the epoxidation of olefins, J. Organometal. Chem. 555, 293-295 (1998).
G. S. Owens, M. M. Abu-Omar, Methyltrioxorhenium-catalyzed epoxidations in ionic liquids, Chem. Commun. 1165-1166 (2000).
G. S. Owens, A. Durazo, M. M. Abu-Omar, Kinetics of MTO-catalyzed olefin epoxidation in ambient temperature ionic liquids: UV/Vis and 2H NMR study, Chem. Eur. J. 8, 3053-3059 (2002).
R. Saladino, V. Neri, A. R. Pelliccia, R. Caminiti, C. Sadun, Preparation and structural characterization of polymer-supported methylrhenium trioxide systems as efficient and selective catalysts for the epoxidation of olefins, J. Org. Chem. 67, 1323-1332 (2002).
O. A. Bouh, J. H. Espenson, Epoxidation reactions with urea-hydrogen peroxide catalyzed by methyltrioxorhenium(VII) on niobia. J. Mol. Cat. A: Chem. 200, 43-47 (2003).
G. Soldaini, F. Cardona, A. Goti, Methyltrioxorhenium ctalyzed domino epoxidationnucleophilic ring opening of glycals, Tetrahedron Lett. 44, 5589-5592 (2003).
A. Goti, F. Cardona, G. Soldaini, C. Crestini, C. Fiani, R. Saladino, Methyltrioxorheniumcatalyzed epoxidation-methanolysis of glycals under homogeneous and heterogeneous conditions, Adv. Synth. Catal. 348, 476-486 (2006).
G. Soldaini, F. Cardona, A. Goti, Catalytic oxidation-phosphorylation of glycals: rate acceleration and enhancement of selectivity with added nitrogen ligands in common organic solvents, Org. Lett. 7, 725-728 (2005).
a) D. E. De Vos, T. Bein, Highly selective epoxidation of alkenes and styrenes with H2O2 and manganese complexes of the cyclic triamine 1,4,7-trimethyl-1,4,7-triazacyclononane, Chem. Commun. 917-918 (1996). b) D. E. De Vos, B. F. Sels, M. Reynaers, Y. V. Subba Rao, P. A. Jacobs, Epoxidation of terminal or electron-deficient olefins with H2O2, catalyzed by Mn-trimethyltriazacyclononane complexes in the presence of an oxalate buffer, Tetrahedron Lett. 39, 3221-3224 (1998).
M. C. White, A. G. Doyle, E. N. Jacobsen, A synthetically useful, self assembling MMO mimic system for catalytic alkene epoxidation with aqueous H2O2, J. Am. Chem. Soc. 123, 7194-7195 (2001).
T. Hori, K. B. Sharpless, Synthetic applications of arylselenenic and arylseleninic acids. Conversion of olefins to allylic alcohols and epoxides, J. Org. Chem. 43, 1689-1697 (1978).
G. J. Ten Brink, B. C. M. Fernandes, M. C. A. van Vliet, I. C. W. E. Arends, R. A. Sheldon, Selenium catalyzed oxidations with aqueous hydrogen peroxide. Part I. Epoxidation reactions in homogeneous solution, J. Chem. Soc. Perkin Trans 1 224-228 (2001).
B. H. Brodsky, J. Du Bois, Oxaziridine-mediated catalytic hydroxylation of unactivated 3°C-H- bonds using hydrogen peroxide, J. Am. Chem. Soc. 127, 15391-15393 (2005).
a) K. Bergstad, S. Y. Jonsson, J. -E. Bäckvall, A new coupled catalytic system for dihydroxylation of olefins by H2O2, J. Am. Chem. Soc. 121, 10424-10425 (1999). b) S. Y. Jonsson, K. Färnegårdh, J.-E. Bäckvall, Osmium-catalyzed asymmetric dihy-droxylation of olefins by H2O2 using a biomimetic flavin-based coupled catalytic system, J. Am. Chem. Soc. 123, 1365-1371 (2001). c) S. Y. Jonsson, H. Adolfsson, J. -E. Bäckvall, MTO and OsO4: an efficient catalytic couple for mild H2O2 based asymmetric dihydroxylation of olefins, Chem. Eur. J. 9, 2783-2788 (2003).
I. W. C. E. Arends, Metal-catalyzed asymmetric epoxidations of terminal olefins using hydrogen peroxide as the oxidant, Angew. Chem. Int. Ed. 45, 6250-6252 (2006).
E. Da Palma Carreiro, G. Young-En, A. J. Burke, Approaches towards catalytic asymmetric epoxidations with methyltrioxorhenium(VII) (MTO): Synthesis and evaluation of chiral non-racemic 2-substituted pyridines, J. Mol. Cat. A.. Chem. 235, 285-292 (2005).
R. I. Kureshy, S. Singh, N. H. Khan, S. H. R. Abdi, I. Ahmed, A. Bhatt, R. V. Jasra, Environmentally friendly protocol for enantioselective epoxidation of non-functionalized alkenes catalyzed by recyclable homochiral dimeric Mn(III) salen complexes with hydrogen peroxide and UHP adduct as oxidants, Catal. Lett. 107, 127-130 (2006).
K. Matsumoto, Y. Sawada, B. Saito, K. Sakai, T. Katsuki, Construction of pseudoheterochiral and homochiral di-μ-oxotitanium (Schiff base) dimers and enantioselective epoxidation using aqueous hydrogen peroxide, Angew. Chem. Int. Ed. 44, 4935-4939 (2005).
Y. Sawada, K. Matsumoto, S. Kondo, H. Watanabe, T. Ozaka, K. Suzuki, B. Saito, T. Katsuki, Titanium-salan-catalyzed asymmetric epoxidation with aqueous hydrogen per-oxide as the oxidant, Angew. Chem. Int. Ed. 45, 3478-3480 (2006).
M. K. Tse, C. Döbler, S. Bhor, M. Klawonn, W. Mägerlein, H. Hugl, M. Beller, Development of a ruthenium-catalyzed asymmetric epoxidation procedure with hydrogen peroxide as the oxidant, Angew. Chem. Int. Ed. 43, 5255-5260 (2004).
M. K. Tse, S. Bhor, M. Klawonn, G. Anilkumar, H. Jiao, A. Spannenberg, C. Döbler, W. Mägerlein, H. Hugl, M. Beller, Ruthenium-catalzyed asymmetric epoxidation of olefins using H2O2, part II: catalytic activities and mechanism, Chem. Eur. J. 12, 1875-1888 (2006).
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Goti, A., Cardona, F. (2008). Hydrogen Peroxide in Green Oxidation Reactions: Recent Catalytic Processes. In: Tundo, P., Esposito, V. (eds) Green Chemical Reactions. NATO Science for Peace and Security Series. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8457-7_9
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DOI: https://doi.org/10.1007/978-1-4020-8457-7_9
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