A new reaction kinetic approach was used to describe the enantioselective hydrogenation of ethyl pyruvate over cinchona-Pt catalyst. The above reaction was considered as the sum of two parallel reactions: (i) racemic hydrogenation resulting in R- and S-product in equal amount and (ii) enantioselective hydrogenation leading to the exclusive formation of one of the two optically isomers. New terms such as accdiff and k e/k r (where k e and k r are the rate constants of the enantioselective and racemic hydrogenation, respectively) were introduced to characterize the relationship between the enantioselective and the racemic hydrogenation reactions. Results obtained show that the formation of R-product is rate accelerated, while the formation of S-product is decelerated. The results indicate also that the overall rate increase is a kinetic phenomenon and cannot be attributed to the suppression of the poisoning effect of CO or oligomers formed from ethyl pyruvate. The strong rate acceleration effect of achiral tertiary amines (ATAs) added to the reaction mixture was attributed to the decrease of the loss of modifier during the hydrogenation experiments.
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References
Y. Orito, S. Imai and S. Niwa, J. Chem. Soc. Japan (1979) 1118
H.U. Blaser H.P. Jalett D.M. Monti J.F. Reber J.T. Wehrli (1988) Stud. Surf. Sci. Catal. 41 153 Occurrence Handle1:CAS:528:DyaL1MXhsFenurg%3D Occurrence Handle10.1016/S0167-2991(09)60810-7
A Baiker (1997) J. Mol. Catal. A: Chem. 115 473 Occurrence Handle1:CAS:528:DyaK2sXks1Ggtw%3D%3D Occurrence Handle10.1016/S1381-1169(96)00352-4
I.M. Sutherland A. Ibbotson R.B. Moyes P.B. Wells (1990) J. Catal. 125 77 Occurrence Handle1:CAS:528:DyaK3cXmtFWitrc%3D Occurrence Handle10.1016/0021-9517(90)90079-Y
R.L. Augustine S.K. Tanielyan L.K. Doyle (1993) Tetrahedron: Asymmetry 4 1803 Occurrence Handle1:CAS:528:DyaK2cXltl2ksA%3D%3D Occurrence Handle10.1016/S0957-4166(00)80422-X
K. Balázsik M. Bartók (2004) J. Catal. 224 463 Occurrence Handle10.1016/j.jcat.2004.03.020 Occurrence Handle1:CAS:528:DC%2BD2cXjvVGisL8%3D
H.U. Blaser, personal communication
H.U. Blaser H.P. Jalett M. Garland M. Studer H. Thies A Wirth-Tijani (1998) J. Catal. 173 282 Occurrence Handle1:CAS:528:DyaK1cXosFWqsA%3D%3D Occurrence Handle10.1006/jcat.1997.1925
H.U. Blaser M. Garland Jalett (1993) J. Catal. 144 569 Occurrence Handle1:CAS:528:DyaK2cXnvFyrtw%3D%3D Occurrence Handle10.1006/jcat.1993.1354
B. Minder M. Schürch T. Mallat A. Baiker (1995) Catal. Lett. 31 143 Occurrence Handle1:CAS:528:DyaK2MXksVegs70%3D Occurrence Handle10.1007/BF00808828
J.L. Margitfalvi M. Hegedűs (1996) J. Mol. Catal. A: Chemical 107 281 Occurrence Handle1:CAS:528:DyaK28XjsVyiurc%3D Occurrence Handle10.1016/1381-1169(95)00220-0
Y. Sun J. Wang C. Leblond R.N. Landau J. Laquidara J.R. Sowa D.G. Blackmond (1997) J. Mol. Catal. A Chem. 115 495 Occurrence Handle10.1016/S1381-1169(96)00353-6
J. Wang Y. Sun C. Leblond R.N. Landau D.G. Blackmond (1996) J. Catal. 161 752 Occurrence Handle1:CAS:528:DyaK28XltVCmurc%3D Occurrence Handle10.1006/jcat.1996.0237
T. Mallat A. Baiker (1998) J. Catal. 176 271 Occurrence Handle1:CAS:528:DyaK1cXjs1Shu7w%3D Occurrence Handle10.1006/jcat.1998.2081
D.G. Blackmond (1998) J. Catal. 176 267 Occurrence Handle1:CAS:528:DyaK1cXjs1Shu78%3D Occurrence Handle10.1006/jcat.1998.2080
T. Mallat Z. Bodnar B. Minder K. Borszeky A. Baiker (1997) J. Catal. 168 183 Occurrence Handle1:CAS:528:DyaK2sXjslSitLc%3D Occurrence Handle10.1006/jcat.1997.1630
J.L. Margitfalvi M. Hegedüs E. Tfirst (1996) Tetrahedron: Asymmetry 7 571 Occurrence Handle1:CAS:528:DyaK28XhsVCmu74%3D Occurrence Handle10.1016/0957-4166(96)00041-9
M. Garland H.U. Blaser (1990) J. Am. Chem. Soc. 112 7048 Occurrence Handle1:CAS:528:DyaK3cXltlWgurc%3D Occurrence Handle10.1021/ja00175a042
H.U. Blaser H.P. Jalett M. Müller M. Studer (1997) Catal. Today 37 441 Occurrence Handle1:CAS:528:DyaK2sXmt1SitL4%3D Occurrence Handle10.1016/S0920-5861(97)00026-6
J.L. Margitfalvi E. Tálas E. Tfirst C.V. Kumar A. Gergely (2000) Appl. Catal. A: Gen. 191 177 Occurrence Handle1:CAS:528:DyaK1MXnvFSmurc%3D Occurrence Handle10.1016/S0926-860X(99)00318-X
J.L. Margitfalvi, E. Tálas and M. Hegedüs, Chem. Commun. (1999) 645
P.B. Wells A.G. Wilkinson (1998) Top. Catal. 5 39 Occurrence Handle1:CAS:528:DyaK1cXjt1GrsbY%3D Occurrence Handle10.1023/A:1019197802585
G. Bond P.A. Meheux A. Ibbotson P.B. Wells (1991) Catal. Today 10 371 Occurrence Handle1:CAS:528:DyaK38XlvFKg Occurrence Handle10.1016/0920-5861(91)80018-5
D.J. Jenkins A.M.S. Alabdulraham G.A. Attard K.G. Griffin P. Johnston P.B Wells (2005) J. Catal. 234 230 Occurrence Handle1:CAS:528:DC%2BD2MXntVymu7o%3D Occurrence Handle10.1016/j.jcat.2005.06.017
D.Y. Murzin P. Maki-Arvela E. Toukoniitty T Salmi (2005) Catal. Rev.-Sci. Eng. 47 175 Occurrence Handle1:CAS:528:DC%2BD2MXkslygsbk%3D
P.N. Rylander (1979) Catalytic Hydrogenation in Organic Syntheses Academic Press New York
D. Ferri T. Bürgi Baiker (2004) J. Phys. Chem. B 108 14384 Occurrence Handle1:CAS:528:DC%2BD2cXks1agtbs%3D Occurrence Handle10.1021/jp049737r
E. Tálas L. Botz J. Margitfalvi O. Sticher A. Baiker (1992) J. Planar Chromatogr. 5 28
J.M. Bonello F.J. Williams A.K. Santra R.M. Lambert (2000) J. Phys. Chem. B 104 9696 Occurrence Handle1:CAS:528:DC%2BD3cXmsVCgtrk%3D Occurrence Handle10.1021/jp002063+
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Margitfalvi, J.L., Tálas, E. & Tfirst, E. Enantioselective hydrogenation of ethyl pyruvate over cinchonidine-Pt/Al2O3 catalyst. A reaction kinetic approach. Top Catal 39, 77–87 (2006). https://doi.org/10.1007/s11244-006-0040-7
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DOI: https://doi.org/10.1007/s11244-006-0040-7