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  A Fully Integrated Continuous-Flow System for Asymmetric Catalysis: Enantioselective Hydrogenation with Supported Ionic Liquid Phase Catalysts Using Supercritical CO2 as the Mobile Phase

Hintermair, U., Franciò, G., & Leitner, W. (2013). A Fully Integrated Continuous-Flow System for Asymmetric Catalysis: Enantioselective Hydrogenation with Supported Ionic Liquid Phase Catalysts Using Supercritical CO2 as the Mobile Phase. Chemistry - A European Journal, 19(14), 4538-4547. doi:10.1002/chem.201204159.

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chem_201204159_sm_miscellaneous_information.pdf (Supplementary material), 840KB
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chem_201204159_sm_miscellaneous_information.pdf
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Supporting Information
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2013
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Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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 Creators:
Hintermair, Ulrich1, Author
Franciò, Giancarlo1, Author
Leitner, Walter2, Author           
Affiliations:
1Institut für Technische und Makromolekulare Chemie RWTH Aachen University, Worringerweg 1, 52074 Aachen (Germany), ou_persistent22              
2Service Department Leitner (Technical Labs), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445626              

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Free keywords: asymmetric catalysis; continuous-flow processing; hydrogenation; ionic liquids; supercritical fluids
 Abstract: A continuous-flow process based on a chiral transition-metal complex in a supported ionic liquid phase (SILP) with supercritical carbon dioxide (scCO2) as the mobile phase is presented for asymmetric catalytic transformations of low-volatility organic substrates at mild reaction temperatures. Enantioselectivity of >99 % ee and quantitative conversion were achieved in the hydrogenation of dimethylitaconate for up to 30 h, reaching turnover numbers beyond 100 000 for the chiral QUINAPHOS–rhodium complex. By using an automated high-pressure continuous-flow setup, the product was isolated in analytically pure form without the use of any organic co-solvent and with no detectable catalyst leaching. Phase-behaviour studies and high-pressure NMR spectroscopy assisted the localisation of optimum process parameters by quantification of substrate partitioning between the IL and scCO2. Fundamental insight into the molecular interactions of the metal complex, ionic liquid and the surface of the support in working SILP catalyst materials was gained by means of systematic variations, spectroscopic studies and labelling experiments. In concert, the obtained results provided a rationale for avoiding progressive long-term deactivation. The optimised system reached stable selectivities and productivities that correspond to 0.7 kg L−1 h−1 space–time yield and at least 100 kg product per gram of rhodium, thus making such processes attractive for larger-scale application.

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Language(s): eng - English
 Dates: 2012-11-212013-03-052013-04-02
 Publication Status: Issued
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.201204159
 Degree: -

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Title: Chemistry - A European Journal
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim, Germany : VCH Verlagsgesellschaft
Pages: 10 Volume / Issue: 19 (14) Sequence Number: - Start / End Page: 4538 - 4547 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058