含光学活性联二萘酚基团可溶性高分子手性配体的合成及其不对称加成反应  

THE SYNTHESIS OF SOLUBLE POLYMER-SUPPORTED CHIRAL BINOL LIGANDS AND ASYMMETRIC ADDITION REACTIONS

作　　者：刘国华[1] 薛允宁[1] 陈晓闽[2] 范青华[2] 

机构地区：[1]上海师范大学生命与环境科学学院化学系,上海200234 [2]中国科学院化学研究所,北京100080

出　　处：《高分子学报》2006年第2期371-376,共6页Acta Polymerica Sinica

基　　金：上海市重点学科建设项目(项目号T0402);上海市科学与技术委员会科学研究项目(项目号05JC14074);上海市教育委员会科学研究项目(项目号05D215)资助项目

摘　　要：Soluble polymeric chiral binaphthol （BINOL） ligands have been synthesized through copolymerization of 3,3′-bis（hydroxymethyl）-2,2′-bis（methoxymethy leneoxy）-1,1′-binaphthyl,1,6-dihydroxyhexane and 1,4-benzene dicarbonyl chloride followed by deprotection of methoxymethyleneoxy groups by iPrOH/HCl,and their application in the enantioselective addition of diethylzinc to benzaldehyde was investigated.All soluble polymeric chiral BINOL ligands were characterized by IR、 1H-NMR、GPC and elemental analysis,which clearly demonstrated the formation of polymeric chiral BINOL ligands.These soluble polymeric chiral ligands were found to be effective in the addition of diethylzinc to benzaldehyde either in the presence or in the absence of Ti（Oi Pr）4 with higher catalytic activities and lower enantioselectivities.In the latter case,the dendritic chiral BINOL ligands showed much higher catalytic activity and a little higher enantioselectivity than BINOLs.Soluble polymeric chiral binaphthol （BINOL） ligands have been synthesized through copolymerization of 3,3＇-his （hydroxymethyl） -2,2＇-his （ methoxymethy leneoxy）- 1, 1＇-binaphthyl, 1,6-dihydroxyhexane and 1,4-benzene diearbonyl chloride followed by deproteetion of methoxymethyleneoxy groups by PrOH/HCl, and their application in the enantioseleetive addition of diethylzine to benzaldehyde was investigated. All soluble polymeric ehiral BINOL ligands were characterized by IR ^1H-NMR,GPC and elemental analysis, which clearly demonstrated the formation of polymeric ehiral BINOL ligands. These soluble polymeric chiral ligands were found to be effective in the addition of diethylzine to benzaldehyde either in the presence or in the absence of Ti（OPr）4 with higher catalytic activities and lower enantioseleetivities. In the latter ease, the dendritic ehiral BINOL ligands showed much higher catalytic activity and a little higher enantioseleetivity than BINOLs.

关 键 词：1 1-联二萘酚 高分子手性催化剂 合成 不对称催化 反应 

分 类 号：O631.3[理学—高分子化学]