Slattery, John Martin orcid.org/0000-0001-6491-8302, Bruce, Duncan Watson orcid.org/0000-0002-1365-2222, Gao, Yanan et al. (2 more authors) (2016) Liquid-Crystalline Ionic Liquids as Ordered Reaction Media for the Diels–Alder Reaction. Chemistry : A European Journal. 16113–16123. ISSN 1521-3765
Abstract
Liquid-crystalline ionic liquids (LCILs) are ordered materials that have untapped potential to be used as reaction media for synthetic chemistry. This paper investigates the potential for the ordered structures of LCILs to influence the stereochemical outcome of the Diels–Alder reaction between cyclopentadiene and methyl acrylate. The ratio of endo- to exo-product from this reaction was monitored for a range of ionic liquids (ILs) and LCILs. Comparison of the endo:exo ratios in these reactions as a function of cation, anion and liquid crystallinity of the reaction media, allowed for the effects of liquid crystallinity to be distinguished from anion effects or cation alkyl chain length effects. These data strongly suggest that the proportion of exo-product increases as the reaction media is changed from an isotropic IL to a LCIL. A detailed molecular dynamics (MD) study suggests that this effect is related to different hydrogen bonding interactions between the reaction media and the exo- and endo-transition states in solvents with layered, smectic ordering compared to those that are isotropic.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2016, Wiley-VCH Verlag GmbH & Co. K. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details. |
Keywords: | DIELS-ALDER,IONIC LIQUID,LIQUID CRYSTAL,MOLECULAR DYNAMICS,Ordered Solvents |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Funding Information: | Funder Grant number THE ROYAL SOCIETY NF080935 THE ROYAL SOCIETY UNSPECIFIED |
Depositing User: | Pure (York) |
Date Deposited: | 04 Oct 2016 10:42 |
Last Modified: | 16 Oct 2024 13:19 |
Published Version: | https://doi.org/10.1002/chem.201602965 |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1002/chem.201602965 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:105544 |
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