| EPSRC Reference: |
GR/T18721/01 |
| Title: |
Molecularly imprinted heterogeneous palladium catalysts |
| Principal Investigator: |
Cammidge, Professor AN |
| Other Investigators: |
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| Researcher Co-Investigators: |
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| Project Partners: |
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| Department: |
Chemistry |
| Organisation: |
University of East Anglia |
| Scheme: |
Standard Research (Pre-FEC) |
| Starts: |
21 April 2005 |
Ends: |
20 April 2008 |
Value (£): |
209,058
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| EPSRC Research Topic Classifications: |
| Catalysis & Applied Catalysis |
Chemical Synthetic Methodology |
| Co-ordination Chemistry |
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Summary on Grant Application Form |
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We envisage that both the efficiency and generality of specific palladium catalysed cross-coupling reactions can be dramatically improved using the molecular imprinting technique. Preliminary results on catalysts designed for use in Suzuki couplings are encouraging and a more rigorous assessment of these systems will be undertaken. Work will then be focused on palladium catalysed amination reactions and molecular imprinting will be exploited to engineer, in a single step, polymer supported palladium/ligand assemblies which incorporate a proximate base. Such assemblies will essentially be biomimetic in that complementary functional groups are placed in a defined arrangement in a reaction cavity . This will serve to:-1. Make the reaction pseudo 2nd order (the base is fixed next to palladium intermediates and has effectively infinite concentration) with associated increase in rate of the desired reaction. 2. Promote N-H deprotonation (leading to amination) over C-H (beta) deprotonation (which leads to starting material reduction) because, again in a biomimetic sense, the base is unable to reach the beta-H. (NB The cavity is filled by substrates preventing solution-phase base, which has a much lower effective concentration anyway, from reaching beta-H). 3. Control monoarylation versus diarylation of primary amines (the steric requirements of the cavity mean that complexation rates of arylated amine will be reduced compared with starting material. (NB Arylation of secondary amines is expected to be faster and more efficient with the Ml ligands compared with the systems currently available. However this rate enhancement will be more pronounced for the primary amines. Differentiation (which has not previously been possible) can therefore be achieved. 4. Promote trans-cis isomerisation thereby offering an additional mechanism for rate enhancement of the desired process. The use of electron rich, hindered ligands will be evaluated with a view to extending the reactions to permit use of aryl chlorides. The influence of bulk-polymer morphology will be assessed.
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Key Findings |
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This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk
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Potential use in non-academic contexts |
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This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk
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Impacts |
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| Description |
This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk |
| Summary |
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| Date Materialised |
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Sectors submitted by the Researcher |
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This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk
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| Project URL: |
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| Further Information: |
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| Organisation Website: |
http://www.uea.ac.uk |