ASYMMETRIC CATALYST DERIVED FROM POLYMER IMOBILIZED CHIRAL 1,2-DIAMINES

源自聚合物固定化手性 1,2-二胺的不对称催化剂

基本信息

批准号：
15550089
负责人：
ITSUNO Shinichi
金额：
$ 2.37万
依托单位：
TOYOHASHI UNIVERSITY OF TECHNOLOGY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550089/
关键词：
1,2-diamine asymmetric hydrogenation ketone chiral monomer polymeric chiral ligand recycle polymer-support

项目摘要

Starting from benzoin derivative we have synthesized new chiral 1,2-diamine having two phenolic hydroxyl groups. This chiral 1,2-diamine was attached to chloromethylated polystyrene. Chiral monomers having 1,2-diamine structure were also prepared and polymerized with styrene and other achiral monomers to give the polymer-supported chiral 1,2-diamine. We have synthesized various kinds of chiral 1,2-diamine monomers. A 1,2-diamine monomer having two p-vinylbenzyl groups as polymerizable group gave the crosslinked polymer. A 1,2-diamine monomer having one p-vinylbenzyl group was polymerized with styrene to give a linear soluble polymer. In the presence of cross-linking agent the insoluble polymer having chiral 1,2-diamine pendant was obtained. Dendritic monomer structure was also introduced and polymerized.In order to evaluate the performance of the polymeric chiral 1,2-diamine ligands, we chose asymmetric hydrogenation of ketone as a model reaction. Chiral complex of 1,2-diamine-BINAP-Ru … More Cl_2 developed by Noyori et al is a powerful tool to obtain optically active secondary alcohols in high level of enantioselectivity. We have prepared the same complex using polymer-supported chiral 1,2-diamine mentioned above. The asymmetric hydrogenation is usually performed in 2-propanol to give the alcohol in quantitative conversion with high enantioselectivity. Unfortunately, no reaction occurred with the polystyrene based polymeric chiral 1,2-diamine ligand mainly due to its shrinkage in the solvent. We found that the mixed solvent of DMF and 2-propanol allowed the hydrogenation using polymeric chiral ligand to give the alcohol. Polymeric catalyst derived from cross-linked polymer having 1,2-diamine pendant showed the best performance in the hydrogenation of ketones. Enantioselectivities attained with this type of polymeric catalyst are almost same as those from the low-molecular-weight catalyst in homogeneous solution system. The insoluble polymeric catalysts could be easily separated from the reaction mixture and recycled many times without loss of catalytic activity. Less

从苯并衍生物开始，我们合成了具有两个酚羟基的新手性1,2-二胺。这种手性1,2-二胺附着在氯甲基化的聚苯乙烯上。还制备了具有1,2-二胺结构的手性单体，并用苯乙烯和其他ACHIRAL单体聚合，从而获得聚合物支持的手性1,2-二胺。我们合成了各种手性1,2二胺单体。 1,2-二胺单体具有两个P-乙烯基苯基作为聚合物组的1,2二胺单体，可提供交联聚合物。用苯乙烯聚合将具有一个P-乙烯基苯基的1,2二胺单体聚合以产生线性固体聚合物。在存在交联剂的情况下，获得了手性1,2-二胺吊坠的不溶性聚合物。为了评估聚合物手性1,2-二胺配体的性能，我们还将树突状单体结构引入并聚合。我们选择酮的不对称氢作为模型反应。 1,2-二胺 - 二甲状腺素的手性复合物…由Noyori等人开发的更多CL_2是一种强大的工具，可在高水平的对映选择性中获得光学活跃的二级醇。我们已经使用上述聚合物支持的手性1,2-二胺制备了相同的复合物。通常在2-丙醇中进行非对称氢化，以高定量转化，并具有高的对映选择性。不幸的是，基于聚苯乙烯的聚合物手性1,2-二胺配体的反应主要是由于溶液中的收缩。我们发现，DMF和2-丙醇的混合溶液允许使用聚合物手性配体氢化液化。来自具有1,2-二胺吊坠的交联聚合物的聚合物催化剂在酮的氢化中表现出最佳性能。这种类型的聚合物催化剂获得的对映选择性与均质溶液系统中低分子量催化剂的催化剂几乎相同。不溶性聚合物催化剂可以很容易地与反应混合物分离，并多次回收而不会丧失催化活性。较少的