(1S,2S)-DPEN修饰的3%Ir/SiO_2/2TPP催化苄叉丙酮的不对称加氢  

Asymmetric Hydrogenation of Benzalacetone Catalyzed by (1S,2S)-DPEN Modified 3%Ir/SiO_2/2TPP Catalysts

作　　者：吴佳蔓[1] 蒋和雁[1] 付海燕[1] 陈华[1] 李瑞祥[1] 李贤均[1] 

机构地区：[1]四川大学化学学院,绿色化学与技术教育部重点实验室,成都610064

出　　处：《物理化学学报》2009年第12期2461-2466,共6页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(20272037)资助项目~~

摘　　要：在温和的条件下制备了负载型3%(w)Ir/SiO2/2TPP(三苯基膦)催化剂,并且考察了(1S,2S)-1,2-二苯基乙二胺[(1S,2S)-DPEN]作为手性修饰剂对其催化苄叉丙酮不对称加氢反应性能的影响.结果表明,手性修饰剂(1S,2S)-DPEN的加入,对苄叉丙酮不对称加氢反应活性和C襒O加氢的选择性都有很好的促进作用.经优化条件,在40℃下,LiOH浓度为0.375mol·L-1的甲醇溶液中,氢气压力为6MPa,反应8h后,苄叉丙酮的转化率大于99.0%,对不饱和醇的选择性大于99.0%,不饱和醇的对映选择性(ee)值达到48.1%.The enantioselective hydrogenation of benzalacetone catalyzed by the chiral diamine [（1S,2S）-1,2-diphenyl-1,2-ethylenediamine]（（1S,2S）-DPEN） modified 3%（w）Ir/SiO2/2TPP（TPP=triphenylphosphine） was investigated.We found that（1S,2S）-DPEN could accelerate the rate of the reaction and efficiently increase the selectivity for C=O bond hydrogenation.Under the optimum reaction conditions,a LiOH concentration of 0.375 mol·L-1 in methanol,a reaction temperature of 40 ℃,a H2 pressure of 6.0 MPa and reaction time of 8 h,the conversion of benzalacetone was more than 99.0% and the selectivity for unsaturated alcohol was more than 99.0%.The enantiomeric excess（ee） value of the unsaturated alcohol reached 48.1%.

关 键 词：不对称加氢 负载型催化剂 手性二胺 苄叉丙酮 铱 

分 类 号：O643.32[理学—物理化学]