主链含双层倍半硅氧烷的C_2-对称双脯氨酰胺手性聚合物催化剂的合成及在不对称Aldol反应中的应用  

C_2-Symmetric Bisprolinamide Chiral Polymer Catalyst with Double Decker Silsesquioxane in Main Chain for the Asymmetric Aldol Reactions

作　　者：沈金瑞 周哲 周远 卢翠芬[1] 杨桂春[1] 陈祖兴[1] SHEN Jinrui ZHOU Zhe ZHOU Yuan LU Cuifen YANG Guichun CHEN Zuxing(School of Chemistry and Chemical Engineering,Hubei Universit)

机构地区：[1]湖北大学化学化工学院,武汉430062

出　　处：《高等学校化学学报》2017年第11期1968-1973,共6页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:51603064)资助~~

摘　　要：以双夹板形的笼型倍半硅氧烷(DDSQ)和叔丁基氧羰基(Boc)保护的C2-对称双脯氨酰胺为底物,通过硅氢加成反应和脱Boc反应,制得主链含DDSQ的C2-对称双脯氨酰胺手性聚合物催化剂;对其化学结构、分子量及热失重性能进行了表征.将制备的聚合物催化剂应用于催化不对称Aldol反应,探讨了其催化性能.结果表明,催化产物均具有较高的产率和立体选择性,且该催化剂便于分离纯化,循环使用6次后催化活性未见明显下降.Double-decker silsesquioxane（DDSQ） and tert-butyl oxygen carbonyl（Boc） protection of C_2-symmetric bisprolinamide were used to prepare C_2-symmetric bisprolinamide chiral polymer catalyst with DDSQ in the main chain. The chiral polymer catalyst was prepared by silicon hydrogen addition reaction and Boc deprotection. The structure of the prepared polymer catalyst was characterized by means of ~1H NMR,^（13）C NMR and ^（29）Si NMR. The molecular weight and thermal property of the prepared polymer catalyst were characterized by means of GPC and TGA. The polymer catalyst was applied in asymmetric Aldol reaction to study the catalytic function,and the products were obtained in good yields and stereoselectivities. Moreover,the polymer catalyst could be readily recovered and recycled for further transformations at least six cycles without observing significant decrease in yield and stereoselectivity.

关 键 词：双夹板形的笼型倍半硅氧烷 C2-对称双脯氨酰胺 手性催化剂 ALDOL反应 

分 类 号：O621.3[理学—有机化学]