新型聚合物微球支载手性诱导试剂的设计、合成及其应用研究

In order to improve the loading capacity of polymer microgel, and explore the polymerization condition and the influencing factor on the structure,characterization, viscocity and supporting effect of polymer microgel,.in this project we first design and synthesize the different generation dendrimers with polyhydroxy, and then prepare the monomer of functionalized styrene with polyhydroxy, which is copolymerized with styrene in solution by choosing appropriate polymerization condition to obtain dendritic microgel with polyhydroxy. The prepared microgel with polyhydroxy is used as soluble polymer support to synthesize polymer microgel supported cyclosulfamide and hydantoin chiral auxiliaries, which are applied in asymmetric alkylation and aldol condensation reactions to investigate the effect of induction and recycling. From the above investigantion, we will develop excellent chiral auxiliaries with high loading, excellent induction effect, easy isolation and purification, and reclying and reusing of the chiral auxiliaries. This design is innovative, and has potential application prospect.

本课题首先设计、合成具有不同代数的含羟基的树状化合物并制备含多羟基苯乙烯类功能单体，选择合适聚合条件，与苯乙烯溶液聚合，制备具有不同容量、可溶和低粘度的含多羟基的树状聚合物微球，以期改善聚合物微球的支载容量，探讨含羟基苯乙烯类功能单体的聚合条件及影响聚合物微球结构、性能、粘度和支载效果的因素。以聚合物微球作为可溶性聚合物载体，合成聚合物微球支载环状磺酰胺和海因类手性诱导试剂，并用于不对称烷基化和羟醛缩合反应中，探讨其不对称诱导性能和回收重复使用效果，寻求具有高的支载容量、良好的不对称诱导效果，方便分离纯化，可回收重复使用的手性诱导试剂。这一设计具有创新性和潜在的应用前景。

本项目制备多羟基苯乙烯功能单体（G2），溶液聚合得到含多羟基的聚苯乙烯微球支载的树状化合物，改善聚合物微球支载量，即使在浓度很低情况下，具有很好的支载容量；以聚苯乙烯微球作为可溶性聚合物载体，合成聚苯乙烯微球支载环磺酰胺和海因手性诱导试剂，并用于不对称烷基化和羟醛缩合反应中，具有很好的不对称诱导效果和回收重复使用性。聚苯乙烯微球支载的手性诱导试剂兼具固相支载合成与经典液相合成的优点，即方便分离纯化，聚合物手性诱导试剂可重复使用，反应快，可用常规的分析手段直接检测反应进程、分离纯度和键合物的结构，能有效地进行不对称诱导，提高光学和化学产率。