极性与二面角双可调型聚苯乙烯-轴手性联苯双膦配体的制备及其拆分氨基酸对映体性能研究

Axially chiral biphenyl diphosphine ligands have good application prospects for the enantioseparation of D/L-amino acids for their good enantio selectivity. But the difficulty of recycle and narrow range of application have restricted its practical application. In this project, polystyrene-axially chiral biphenyl diphosphine ligands with tunable polarity and dihedral angle were synthesized. These new ligands have the advantages of: (1) diphosphine ligands are recycled by loading on polystyrene; (2) good mass transfer performance and low achiral adsorption capacity of amino acids are obtained by controlling the polarity of polystyrene; (3) the application range of ligands are expanded by regulating the dihedral angles. The influences of polarity on mass transfer performance and achiral adsorption capacity of amino acid, and dihedral angles on enantio selectivity of ligands toward D/L-amino acid are both investigated. Furthermore, the chiral recognition mechanism between ligands and D/L-amino acid is also disclosed on the basis of their spatial configurations. This project will make ligand recyclable and expand the application range of ligands. And it will supply important theoretical guidance and reference for synthesizing novel axially chiral biphenyl diphosphine ligands in future work.

轴手性双膦配体因其良好的手性识别能力，在拆分氨基酸对映体方面表现出了良好的应用前景，但拆分过程中配体回收困难、配体适用范围窄，制约了该类配体的实际应用。本项目拟以极性可控聚苯乙烯树脂为载体,对二面角可调轴手性联苯双膦配体进行负载，制备极性与二面角双可调型聚苯乙烯-轴手性联苯双膦配体。该配体的优点是：（1）配体负载于聚苯乙烯，可实现回收；（2）树脂极性可控，使氨基酸传质性能优良且非手性吸附容量较小；（3）可通过调控配体二面角，拓宽配体的适用范围。研究过程中着重探讨聚苯乙烯极性对氨基酸传质性能与非手性吸附容量的影响，以及配体二面角对配体识别氨基酸对映体性能的影响，并结合配体与氨基酸的立体构型关系，探明轴手性联苯双膦配体识别氨基酸对映体的机理。本项目的实施可解决轴手性联苯双膦配体回收困难、适用范围窄的问题，且能为今后新型轴手性双膦配体的开发提供理论指导和借鉴依据。

液液手性萃取是获取单一对映体的一种重要方法，如何实现手性萃取剂的回收及拓展手性萃取剂的种类一直是该领域的研究重点。本项目主要完成了以下研究工作：（1）以聚苯乙烯树脂为载体对双膦配体进行了负载固定，实现氨基酸对映体拆分过程中双膦配体的回收利用；（2）制备了一系列二面角可调的轴手性联苯双膦配体，探讨了配体二面角对配体识别氨基酸对映体性能的影响，通过调控配体二面角实现了各氨基酸对映体的良好拆分；（3）结合配体与氨基酸对映体的立体构型关系，提出了轴手性联苯双膦配体识别氨基酸对映体可能的机理；（4）依据双膦配体识别氨基酸对映体的机理，以(S,S)-DIOP、(S)-SDP和Mandyphos为配体与金属离子络合实现了3-氯-苯甘氨酸或4-硝基-苯丙氨酸的良好拆分，进一步丰富了手性萃取剂的种类。本项目的实施实现了液液手性萃取过程中轴手性双膦配体的回收，拓展了手性萃取剂的种类，并提出了相关的识别机理，为今后新型手性萃取剂的设计开发提供了理论指导和借鉴依据。