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

多组分多步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。这些方法中的许多都需要多功能均相催化剂。将均相催化剂固定在载体上克服了分离和重复使用的固有问题。该项目旨在开发用于膜反应器中均相催化的新型固定化配体系统。固定化是通过可溶的、(超)可过滤的和可重复使用的树枝状聚甘油和构建功能壳来实现的。首先用一些非手性和手性标准配体测试了这些体系在原理证明方面的应用。通过将丙烯腈Michael加成/腈还原序列(Vögtle法)与氢甲酰化/还原胺化(氢氨甲基化)相结合，规划了新的收敛的树状大分子和树枝状合成。具有P或N/O官能团的树枝末端封端，包括具有对映体纯度的体系，为催化剂的固定化提供了配体。此外，还计划根据上述方法合成、催化评价新的手性体系，并将其固定在树枝状聚甘油和多胺上。新的固定化配体将在膜反应器或类似的流动系统中进行测试，用于连续生产或通过均相催化进行库合成，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.