New Recyclable Phosphorous Ligands for Regio- and Stereocontrol in Homogeneous Catalysis

多组分、多步骤转化作为一锅反应序列是现代合成化学中极具吸引力的工具。许多这些方法需要多功能均相催化剂。均相催化剂在载体上的固定化克服了分离和再利用的固有问题。该项目旨在开发用于膜反应器均相催化的新型固定化配体系统。固定化是通过可溶性，（超）过滤和可重复使用的树突状聚甘油和功能壳的构建来实现的。首先用一些非手性和手性标准配体测试了这些系统在原理证明中的应用。通过丙烯腈Michael加成/腈还原序列（Vögtle方法）与氢甲酰化/还原性胺化（氢氨甲基化）的组合，计划了新的收敛树突和树突合成。末端带有P或N/O功能的树突，包括对映体纯体系，为催化剂固定化提供了配体。在此基础上，规划了新的P产氧体系的合成、催化评价及其在枝状聚甘油和多胺上的固定化。新的固定化配体将在膜反应器或类似的流动系统中进行连续生产或通过均相催化进行文库合成，以实现新的可持续工艺。

Multi-component and multi-step conversions as one-pot reaction sequences are attractive tools in modern synthetic chemistry. Many of these methods require multifunctional homogeneous catalysts. Immobilization of homogeneous catalysts on supports overcomes the inherent problems of separation and reuse. The project aims at development of novel immobilized ligand systems for homogeneous catalysis in membrane reactors. Immobilization is achieved with soluble, (ultra)filterable and reusable dendritic polyglycerols and the construction of functional shells. Applications of these systems for proof of principle is first tested with some achiral and chiral standard ligands. New convergent dendrimer and dendron syntheses are planned via combinations of acrylonitrile Michael addition/nitrile reduction sequences (Vögtle method) with hydroformylation/reductive amination (hydroaminomethylation). Endcapping of the dendrons with P or N/O functionalities including enantiomerically pure systems supplies the ligands for catalyst immobilization. Furthermore synthesis, catalytic evaluation of new P chirogenic systems is planned as well as their immobilization to dendritic polyglycerols and polyamines according to the above mentioned methods. The new immobilized ligands are to be tested in membrane reactors or similar flow systems for continuous production or library syntheses via homogeneous catalysis in order to realize new sustainable processes.