Merrifield树脂负载L-脯氨酸催化不对称Aldol反应  

Merrifield Resin Prepared by Graft Diamine Load L-proline Catalyst and Catalytic Performance for Asymmetric Aldol Reaction

作　　者：王晶[1] 赵文善[1] 吴玉峰[1] 崔元臣[1,2] 

机构地区：[1]河南大学化学化工学院,河南开封475004 [2]河南大学特种功能材料教育部重点实验室,河南开封475004

出　　处：《河南大学学报（自然科学版）》2015年第6期666-672,共7页Journal of Henan University:Natural Science

基　　金：河南省自然科学基金项目(082300420010)

摘　　要：利用乙二胺、丁二胺、己二胺、辛二胺、癸二胺和十二烷二胺作为Merrifield树脂与L-脯氨酸的连接臂,制备了一系列负载型L-脯氨酸催化剂,以水介质中的不对称Aldol反应为模型,考察了连接臂碳链的长短对催化剂性能的影响.研究表明:以碳链长度最短的乙二胺作为连接臂制备的催化剂4a催化性能较好,可使不对称Aldol反应获得较好的立体选择性,其中dr值为31∶69,ee值为91%,且催化剂4a在水介质中的催化性能明显优于在有机溶剂中的催化性能.进一步研究了催化剂用量、水用量、底物等因素对催化剂4a催化性能的影响,发现催化剂用量为1mol%、水用量为0.1mL、环己酮用量为醛的5倍当量(0.129mL)时,不对称Aldol反应产物的dr值为24∶76,ee值为90%.催化剂4a还具有一定的底物适用性能和较好的重复使用性能.A series of Merrifield resin supported L-proline catalysts were prepared using ethylenediamine,butanediamine,hexanediamine,octanediamine,decamethylene diamine or dodecane diamine as connecting arm respectively.The influence of carbon chain lengths of the connecting arm on catalytic performance was investigated by utilizing asymmetric Aldol reaction in water as model reaction.It was found that catalyst 4aprepared with the shortest length of the carbon chain ethylenediamine as the connecting arm showed good catalytic performance for asymmetric Aldol reaction in water at room temperature.As a result,better diastereoselectivity（31∶69）and enantioselectivity（91%）could be achieved.The catalytic performance of catalyst 4ain aqueous media was superior to the catalytic properties in organic solvents.The effects of the dosage of catalyst,water consumption and the substrate on catalytic performance of the catalyst 4a were further investigated.When the optimum amount of catalyst was 1mol%,water in an amount of 0.1mL and cyclohexanone in an amount of 5equivalents（0.129mL）of an aldehyde,the product with excellent diastereoselectivity（up to 24∶76）and enantioselectivity（90%）was obtained.In addition,the catalyst could be recovered through simple filtration,and the catalyst 4acould be re-used for four times without obvious loss of catalytic activity and stereochemical reactivity.

关 键 词：二元胺 Merrifield树脂 L-脯氨酸 ALDOL反应 

分 类 号：O633.223[理学—高分子化学]