Continuous flow hydrosilylation in SILP/scCO2 systems - an innovative approach to reduction andfunctionalization of alkynes, imines and carbonyl compounds

SILP/scCO2 系统中的连续流氢化硅烷化 - 一种减少炔烃、亚胺和羰基化合物并使其官能化的创新方法

• 批准号: 426583288
• 负责人: Dr. Giancarlo Franciò
• 金额: --
• 依托单位: Narodowe Centrum Nauki
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2019
• 资助国家: 德国
• 起止时间: 2018-12-31 至 2023-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/426583288?language=en
• 关键词: Continuous; flow; hydrosilylation; SILP; scCO2

The goal of the project is to design, evaluate, and demonstrate methods for continuous-flow catalytic hydrosilylation of molecules bearing C≡C, C=O and C=N bonds. For this purpose, catalytic systems comprising molecular catalysts or catalytically active nanoparticles stabilized and immobilized in a supported ionic liquid phase (SILP) or on Phosphotungstic Acid (PTA)/aluminum oxide (Alox) supports will be developed. Stereoselective versions are envisaged too by using molecular catalysts with chiral ligands. In the SILP-scCO2 approach, supercritical carbon dioxide (scCO2) will be used as a mobile phase to transport substrates into the catalyst containing SILP matrix and simultaneously extract the products for isolation. This methodology takes advantagefrom the gas-like transport and liquid-like solubility properties of scCO2. Thanks to the high solubility of organosilicon compounds in compressed carbon dioxide and the negligible solubility of the SILP materials in the same medium, this approach is particularly suited for the envisaged application. In the case of the (PTA)/Alox approach, the use of neat reagents, scCO2 or conventional solvents will be used to realize the flow depending on the nature of the substrates/products. This study will provide fundamental knowledge on the combination ofcatalysis with advanced fluids, thus contributing to a general progress in the understanding,control, and mastering of continuous-flow processes at the three different, yet stronglyinterconnected, process levels:- Molecular scale: How do the molecular interactions of catalytically active metal complexes and clusters with the immobilization matrix affect their performance on the short and on the long term?- Mesoscale: How do the physico-chemical properties of the catalyst, subtrates andproducts harmonize with the stationary and mobile phase and, in general, with the devised strategy for integrating reaction and separation?- Macroscale: How should a compact continuous-flow setup be designed and constructed to implement the devised reaction/separation approach and to allow both reaction and catalyst monitoring?The exploitation of these three levels with a focus on mutual compatibility will result in a new sustainable approach for catalytic organosilicon chemistry leading to high productivities and improved or even novel selectivities. The combination of flow-chemistry using scCO2 as benign transport medium with an effective catalyst immobilization procedure will ensure metal-free and solvent-free product isolation, thus cutting down any additional tedious or material intensive workup procedures. We aim at a flexible methodology enabling the continuous flow hydrosilylation of various alkynes and carbonyl compounds with minor operational adjustments.

该项目的目标是设计、评估和演示带有 C=C、C=O 和 C=N 键的分子的连续流动催化氢化硅烷化方法。为此，包含稳定的分子催化剂或催化活性纳米颗粒的催化系统。将开发固定在负载离子液体相（SILP）或磷钨酸（PTA）/氧化铝（Alox）载体上的材料。立体选择性版本也可以通过使用具有手性配体的分子催化剂来实现。在 SILP-scCO2 方法中，超临界二氧化碳 (scCO2) 将用作流动相，将底物输送到含有 SILP 基质的催化剂中，同时提取产物进行分离。该方法利用了 scCO2 的类气体传输和类液体溶解度特性，这要归功于有机硅化合物在压缩二氧化碳中的高溶解度和可忽略不计的溶解度。由于 SILP 材料在相同介质中的溶解度不同，该方法特别适合设想的应用。在 (PTA)/Alox 方法中，将使用纯试剂、scCO2 或常规溶剂来实现取决于流量。这项研究将提供有关催化与先进流体相结合的基础知识，从而有助于在三种不同但尚未实现的连续流过程的理解、控制和掌握方面取得总体进展。强相互关联的工艺水平：- 分子尺度：催化活性金属配合物和簇与固定基质的分子相互作用如何影响其短期和长期性能？- 介观尺度：催化活性金属配合物和簇的分子相互作用如何影响其短期和长期性能？催化剂、底物和产物与固定相和流动相协调一致，并且一般而言，与整合反应和分离的设计策略协调一致？-宏观尺度：如何设计和构建紧凑的连续流装置实施设计的反应/分离方法并允许反应和催化剂监测？以相互兼容性为重点的这三个水平的开发将为催化有机硅化学带来新的可持续方法，从而提高生产率和改进甚至新颖的选择性使用 scCO2 作为良性传输介质的流动化学与有效的催化剂固定程序相结合，将确保无金属和无溶剂的产品分离，从而减少任何额外的繁琐或材料密集型后处理我们的目标是采用灵活的方法，通过少量的操作调整即可实现各种炔烃和羰基化合物的连续流动氢化硅烷化。