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Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
An artificial metalloenzyme for olefin metathesis.
Clemens Mayer1, Dennis G Gillingham, Thomas R Ward
1Laboratory of Organic Chemistry, ETH Zürich, 8093 Zürich, Switzerland.
Chemical Communications (Cambridge, England)
|October 13, 2011
Summary
Researchers created a novel artificial metalloenzyme by modifying a heat shock protein with a Grubbs-Hoveyda catalyst. This new metalloenzyme demonstrates catalytic activity in olefin metathesis reactions under acidic conditions.
Area of Science:
- Biochemistry
- Organic Chemistry
- Catalysis
Background:
- Small heat shock proteins (sHSPs) play crucial roles in cellular protection.
- Olefin metathesis is a powerful carbon-carbon bond-forming reaction.
- Artificial metalloenzymes combine the selectivity of proteins with the reactivity of metal catalysts.
Purpose of the Study:
- To engineer a novel artificial metalloenzyme by functionalizing a small heat shock protein.
- To investigate the catalytic activity of the modified protein in olefin metathesis reactions.
- To assess the performance of the artificial metalloenzyme under acidic conditions.
Main Methods:
- Modification of a cysteine-containing variant of Methanocaldococcus jannaschii small heat shock protein.
- Attachment of a Grubbs-Hoveyda type olefin metathesis catalyst via an electrophilic bromoacetamide linker.
- Evaluation of the resulting artificial metalloenzyme in a benchmark ring closing metathesis reaction.
Main Results:
- Successful creation of an artificial metalloenzyme by covalently linking a Grubbs-Hoveyda catalyst to a small heat shock protein.
- The artificial metalloenzyme exhibited catalytic activity in a ring closing metathesis reaction.
- The catalyst demonstrated functionality under acidic conditions, expanding its operational range.
Conclusions:
- Small heat shock proteins can be effectively engineered into artificial metalloenzymes.
- The developed artificial metalloenzyme offers a promising platform for catalytic applications in acidic environments.
- This work highlights the potential of integrating protein scaffolds with transition metal catalysts for novel reactivity.
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