以介孔材料SBA-15、经或未经Al2O3修饰的具有三维立方孔道结构的SiO2为载体,制备了负载型Pt催化剂,并用于催化α-酮酸酯底物2-氧代-4-苯基-丁酸乙酯(EOPB)和丙酮酸乙酯(Etpy)的不对称氢化反应中.结果表明,当SBA-15孔径由6.2,7.6和9.2nm依次增加时,EOPB不对称氢化的活性和手性选择性有所提高,氢化ee值分别为22.0%,36.0%和50.0%.两类拥有三维立方孔道结构的SiO2载体负载的Pt催化剂性能明显优于SBA-15负载的,表明传质或空间位阻因素对EOPB不对称氢化的手性选择性和反应活性影响很大.以Al2O3修饰的介孔硅为载体时,相应的Pt催化剂上EOPB氢化手性选择性最高(ee 79.3%),且具有高氢化活性;用于丙酮酸乙酯不对称氢化反应时,活性和手性选择性(ee值达90.2%以上)均较高.由此可见,Al2O3修饰的三维立方介孔硅结构的复合纳米材料是一种新型的多相手性催化剂载体,具有良好的应用前景.
参考文献
[1] | Rouhi A M .[J].Chemical and Engineering News,2003,81:45. |
[2] | Rouhi A M .[J].Chemical and Engineering News,2004,82:47. |
[3] | Zhang W C;Zhang X M .[J].Angewandte Chemie International Edition,2006,45:5515. |
[4] | 李晓东,吕士杰,陈新滋.修饰型多相手性催化剂在不对称合成中的应用[J].化学进展,2001(01):33-42. |
[5] | 刘启宾,周永贵.铱催化 3-羟甲基-2H-苯并吡喃类化合物的不对称氢化[J].催化学报,2007(10):847-849. |
[6] | Li C .Chiral synthesis on catalysts immobilized in microporous and mesoporous materials[J].Catalysis Reviews. Science and Engineering,2004(3/4):419-492. |
[7] | Mallat T;Orglmeister E;Balker A .[J].Chemical Reviews,2007,107:4863. |
[8] | Mondelli C;Vargas A;Santarossa G;Baiker A .[J].Journal of Physical Chemistry C,2009,113:15246. |
[9] | Tai A;Sugimura T;De Vos D E;Vankelecom I F J,Jacobs P A eds.Chiral Catalyst Immobilization and Recycling[M].Weinheim:Wiley-VCH,2000:173. |
[10] | Blaser H U;Jalett H P;Wiehl J .[J].Journal of Molecular Catalysis,1991,68:215. |
[11] | Osawa T;Harada T;Tai A .[J].Catalysis Today,1997,37:465. |
[12] | Tálas, E.;Margitfalvi, J.L.;Egyed, O. .Additional data to the origin of rate enhancement in the enantioselective hydrogenation of activated ketones over cinchonidine modified platinum catalyst[J].Journal of Catalysis,2009(2):191-198. |
[13] | Studer M;Blaser H U;Exner C .[J].Advanced Synthesis and Catalysis,2003,45:345. |
[14] | 李晓红,李灿.多相不对称催化氢化研究进展[J].化学进展,2003(03):204-214. |
[15] | Baiker A;Blaser H U;Erlt G;Kn(E)zinger H,Weitkamp J eds.Handbook of Heterogeneous Catalysis[M].Weiheim:Wiley-VCH,1997:121. |
[16] | 明方永,王金波,付海燕,陈骏,陈华,李贤均.手性二胺修饰的Ru-TPP/γ-Al2O3催化苄叉丙酮不对称加氢反应[J].催化学报,2007(12):1057-1061. |
[17] | 韩涤非,杨启华,李灿.表面上和纳米孔道内以及乳液中的手性催化[J].催化学报,2008(09):789-816. |
[18] | Yang C F;Jiang H Y;Feng J;Fu H Y Li R X Chen H Li X J .[J].Journal of Molecular Catalysis A:Chemical,2009,300:98. |
[19] | Orito Y;Imai S;Niwa S.[A].Japan,1978:130. |
[20] | Raynor S A;Thomas J M;Raja R;Johnson B F G,Bell R G,Mantle M D.[J].Chemical Communications,2000:1925. |
[21] | Raja R;Thomas J M;Jones M D;Johnson B F G Vaughan D E W .[J].Journal of the American Chemical Society,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 .[J].Angewandte Chemie International Edition,2003,42:4326. |
[23] | Zhang HD;Xiang S;Li C .Enantioselective epoxidation of unfunctionalised olefins catalyzed by Mn(salen) complexes immobilized in porous materials via phenyl sulfonic group[J].Chemical communications,2005(9):1209-1211. |
[24] | Zbang H D;Xiang S;Xiao J L;Li C .[J].Journal of Molecular Catalysis A:Chemical,2005,238:175. |
[25] | Li C;Zhang HD;Jiang DM;Yang QH .Chiral catalysis in nanopores of mesoporous materials[J].Chemical communications,2007(6):547-558. |
[26] | 马红霞,杨超,陈华,李贤均.预处理和修饰条件对负载型铑纳米簇催化丙酮酸甲酯不对称加氢性能的影响[J].催化学报,2003(08):619-623. |
[27] | Minder B;Mallat T;Skrabal P;Baiker A .[J].Catalysis Letters,1994,29:115. |
[28] | Burgi T.;Baiker A. .Model for enantioselective hydrogenation of alpha-ketoesters over chirally modified platinum revisited: Influence of alpha-ketoester conformation[J].Journal of Catalysis,2000(2):445-451. |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分:
-
10%
-
20%
-
30%
-
40%
-
50%