Synthesis and Catalytic Application of Knölker-Type Iron Complexes with a Novel Asymmetric Cyclopentadienone Ligand Design
| Autor: | Darya Hadavi, Khi Chhay Chou, Lukas Morick, Burgert Blom, Christian A. M. R. van Slagmaat, Stefaan M. A. De Wildeman |
|---|---|
| Přispěvatelé: | RS: FSE Biobased Materials, Biobased Materials, Imaging Mass Spectrometry (IMS), RS: M4I - Imaging Mass Spectrometry (IMS), Maastricht Science Programme, RS: FSE MSP, RS: FSE AMIBM |
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
COOPERATIVE TRANSITION-METAL
MEDIATED 2+2+1 CYCLOADDITIONS TRICARBONYL COMPLEXES Homogeneous catalysis CHIRAL BRONSTED ACID lcsh:Chemical technology 010402 general chemistry 01 natural sciences DFT Catalysis lcsh:Chemistry chemistry.chemical_compound iron NMR spectroscopy structural design KETONES lcsh:TP1-1185 Physical and Theoretical Chemistry EXCHANGE REACTION CARBON-MONOXIDE Science & Technology Chemistry Physical 010405 organic chemistry Ligand Asymmetric hydrogenation Enantioselective synthesis conformational analysis METAL-DIENE COMPLEXES Nuclear magnetic resonance spectroscopy ORGANIC-SYNTHESIS ENANTIOSELECTIVE HYDROGENATION Combinatorial chemistry asymmetric hydrogenation homogeneous catalysis 0104 chemical sciences Chemistry lcsh:QD1-999 chemistry Physical Sciences Enantiomer Acetophenone |
| Zdroj: | Catalysts Volume 9 Issue 10 Catalysts, Vol 9, Iss 10, p 790 (2019) Catalysts, 9(10):790. Multidisciplinary Digital Publishing Institute (MDPI) |
| ISSN: | 2073-4344 |
| Popis: | Asymmetric catalysis is an essential tool in modern chemistry, but increasing environmental concerns demand the development of new catalysts based on cheap, abundant, and less toxic iron. As a result, Knö lker-type catalysts have emerged as a promising class of iron catalysts for various chemical transformations, notably the hydrogenation of carbonyls and imines, while asymmetric versions are still under exploration to achieve optimal enantio-selectivities. In this work, we report a novel asymmetric design of a Knö lker-type catalyst, in which the C2-rotational symmetric cyclopentadienone ligand possesses chiral substituents on the 2- and 5-positions near the active site. Four examples of the highly modular catalyst design were synthesized via standard organic procedures, and their structures were confirmed with NMR, IR, MS, and polarimetry analysis. Density functional theory (DFT) calculations were conducted to elucidate the spatial conformation of the catalysts, and therewith to rationalize the influence of structural alterations. Transfer- and H2-mediated hydrogenations were successfully established, leading to appreciable enantiomeric excesses (ee) values up to 70%. Amongst all reported Knö lker-type catalysts, our catalyst design achieves one of the highest ee values for hydrogenation of acetophenone and related compounds. |
| Databáze: | OpenAIRE |
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