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.

该项目的目的是设计，评估和演示轴承分子的连续流催化氢化化的方法，C = O和C = N键。为此，将开发催化系统，包括分子催化剂或催化活性的纳米颗粒稳定并固定在受支持的离子液相（SILP）或磷酸烟酸（PTA）/氧化铝（Alox）上的催化系统。也通过使用手性配体的分子催化剂来设想立体选择版。在SILP-SCCO2方法中，超临界二氧化碳（SCCO2）将用作流动相，以将基板运输到含有SILP基质的催化剂中，并简单地提取产物进行分离。该方法从SCCO2的气状运输和液体样的可溶性中利用了优势。感谢有机硅化合物在压缩二氧化碳中的高溶液和在同一培养基中SILP材料的可忽略不计的溶液，这种方法特别适合于设想的应用。在（PTA）/ALOX方法的情况下，使用纯试剂，SCCO2或常规溶液的使用将根据底物/产品的性质实现流量。 This study will provide fundamental knowledge on the combination of catalysis with advanced fluids, thus contributing to a general progress in the Understanding,control, and mastering of continuous-flow processes at the three different, yet strongly interconnected, 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催化剂，亚底物和产品的物理化学特性是否与固定和流动阶段保持一致，并且一般而言，与整合反应和分离的设计策略？ - 宏观：宏观：如何设计和构建紧凑型连续流程设置，以实现设计的反应/分离方法，并允许对这些型号进行启用，以构成这些级别的范围？催化有机硅化学导致高产物，改善甚至新颖的选择性。使用SCCO2作为良性传输培养基与有效的催化剂固定程序的流量化学结合将确保无金属和无溶剂的产品隔离，从而减少任何其他繁琐或物质强化的强化工作程序。我们的目标是一种灵活的方法，使各种炔烃和羰基化合物的连续流氢硅化具有较小的操作调整。