DOI: 10.3724/SP.J.1088.2011.00921

Chinese Journal of Catalysis (催化学报) 2011/32:1 PP.155-161

Enantioselective Hydrogenation of α-Ketoesters on Mesoporous Matrix Supported Platinum Catalysts

The asymmetric hydrogenation of ethyl 2-oxo-4-phenyl-butyrate (EOPB) over the Pt catalysts modified by cinchonidine using mesoporous SBA-15, cubic mesoporous silica, and Al2O3 modified cubic mesoporous silica as matrix was studied. The results showed that in the channels of mesoporous SBA-15, the enantioselectivity and conversion are enhanced in larger sized channels compared to those of the hydrogenation in smaller sized channels. When the channel size of SBA-15 increases from 6.2 nm to 7.6 nm and to 9.2 nm, the hydrogenation ee is 22.0%, 36.0%, and 50.0%, respectively. The ee (53.8%) on the cubic mesoporous silica support is obviously higher than that (36.0%) on the SBA-15 support with similar channel size, and the ee on the Al2O3 modified cubic mesoporous silica support reaches 79.3%. These facts showed that the mass transfer or steric clash has important impacts on the enantioselectivity and conversion of the enantioselective hydrogenation of EOPB. In the enantioselective hydrogenation of ethyl pyruvate, the Al2O3-grafted cubic mesoporous silica supported Pt catalyst exhibits high activity and excellent enantioselectivity (ee over 90.2%), which is comparable to that of the best commercial Pt/Al2O3 catalysts. The high catalytic performance is attributed not only to the developed cubic channel structure of the Pt catalyst support, but also to the enhancement of the interaction of Pt nanoparticles and the Al2O3-grafted support, which would improve the modification of cinchonidine on the surface of Pt particles. These indicate that the Al2O3 modified cubic mesoporous silica is a novel, promising support material for the heterogeneous chiral catalysis.

Key words:mesoporous matrix,platinum catalyst,cinchonidine,chiral modification,ethyl 2-oxo-4-phenyl-butyrate,ethyl pyruvate,enantioselective hydrogenation

ReleaseDate:2014-07-24 00:22:20

1 Rouhi A M. Chem Eng News, 2003, 81: 45

2 Rouhi A M. Chem Eng News, 2004, 82: 47

3 Zhang W C, Zhang X M. Angew Chem, Int Ed, 2006, 45: 5515

4 李晓东, 吕士杰, 陈新滋. 化学进展 (Li X D, Lü Sh J, Chen X Z. Progr Chem), 2001, 13: 33

5 刘启宾, 周永贵. 催化学报 (Liu Q B, Zhou Y G. Chin J Catal), 2007, 28: 847

6 Li C. Catal Rev, 2004, 46: 419

7 Mallat T, Orglmeister E, Baiker A. Chem Rev, 2007, 107: 4863

8 Mondelli C, Vargas A, Santarossa G, Baiker A. J Phys Chem C, 2009, 113: 15246

9 Tai A, Sugimura T. In: De Vos D E, Vankelecom I F J, Jacobs P A eds. Chiral Catalyst Immobilization and Recycling. Weinheim: Wiley-VCH, 2000. 173

10 Blaser H U, Jalett H P, Wiehl J. J Mol Catal, 1991, 68: 215

11 Osawa T, Harada T, Tai A. Catal Today, 1997, 37: 465

12 Tálas E, Margitfalvi J L, Egyed O. J Catal, 2009, 266: 191

13 Studer M, Blaser H U, Exner C. Adv Synth Catal, 2003, 45: 345

14 李晓红, 李灿. 化学进展 (Li X H, Li C. Progr Chem), 2003, 15: 204

15 Baiker A, Blaser H U. In: Erlt G, KnÊzinger H, Weitkamp J eds. Handbook of Heterogeneous Catalysis. Vol. 5. Weiheim: Wiley-VCH, 1997. 121

16 明方永, 王金波, 付海燕, 陈骏, 陈华, 李贤均. 催化学报 (Ming F Y, Wang J B, Fu H Y, Chen J, Chen H, Li X J. Chin J Catal), 2007, 28: 1057

17 韩涤非, 杨启华, 李灿. 催化学报 (Han D F, Yang Q H, Li C. Chin J Catal), 2008, 29: 789

18 Yang C F, Jiang H Y, Feng J, Fu H Y, Li R X, Chen H, Li X J. J Mol Catal A, 2009, 300: 98

19 Orito Y, Imai S, Niwa S. Preprints of the 43rd Catalysis Forum. Japan, 1978. 130

20 Raynor S A, Thomas J M, Raja R, Johnson B F G, Bell R G, Mantle M D. Chem Commun, 2000: 1925

21 Raja R, Thomas J M, Jones M D, Johnson B F G, Vaughan D E W. J Am Chem Soc, 2003, 125: 14982

22 Jones M D, Raja R, Thomas J M, Johnson B F G, Lewis D W, Rouzaud J, Harris K D M. Angew Chem, Int Ed, 2003, 42: 4326

23 Zhang H D, Xiang S, Li C. Chem Commun, 2005: 1209

24 Zhang H D, Xiang S, Xiao J L, Li C. J Mol Catal A, 2005, 238: 175

25 Li C, Zhang H D, Jiang D M, Yang Q H. Chem Commun, 2007: 547

26 马红霞, 杨超, 陈华, 李贤均. 催化学报 (Ma H X, Yang Ch, Chen H, Li X J. Chin J Catal), 2003, 24: 619

27 Minder B, Mallat T, Skrabal P, Baiker A. Catal Lett, 1994, 29: 115

28 Burgi T, Baiker A. J Catal, 2000, 194: 445