EPSRC Reference: |
GR/N05208/01 |
Title: |
DETECTING, UNDERSTANDING, CONTROLLING AND EXPLOITING 'MEMORY EFFECTS' IN PD-CATALYSED ALLYLATION |
Principal Investigator: |
Lloyd-Jones, Professor G |
Other Investigators: |
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Researcher Co-Investigators: |
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Project Partners: |
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Department: |
Chemistry |
Organisation: |
University of Bristol |
Scheme: |
Standard Research (Pre-FEC) |
Starts: |
06 March 2000 |
Ends: |
05 July 2003 |
Value (£): |
185,047
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EPSRC Research Topic Classifications: |
Catalysis & Applied Catalysis |
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EPSRC Industrial Sector Classifications: |
Chemicals |
Pharmaceuticals and Biotechnology |
No relevance to Underpinning Sectors |
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Related Grants: |
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Panel History: |
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Summary on Grant Application Form |
By impeding full ligand control, memory effects can compromise regio- and enantio-selectivity in Pd-catalysed allylic alkylation. Their mechanistic origins are diverse and not well understood. Moreover, the presence of a stereochemical memory effect can often be hard to detect - even if its effect is large. Consequently, conclusions drawn about ligand efficacy (particularly new ligands) can be invalid and misleading. The research programme has three objectives: The detection (stage 1), understanding (stage 2) and control and exploitation (stage 3) of memory effects.Stage 1: development of simple but effective methods for the detection of memory effects. In addition to being a prerequisite to stage 2., the methods developed will be employable by other workers in the field.Stage 2: physical-organic investigation (including UV/reaction calorimetry kinetics, 1 and 2D high field NMR and isotopic labelling) allowing an understanding of the mechanistic origins of the memory effects.Stage 3: testing our understanding by developing methods for the control (elimination) of memory effects. This will include: solvent effects, rates and orders of addition, ion-pairing/asymmetric ion-pairing, counter-ion effects and ligand design/synthesis. In addition, memory effects will also be deliberately engendered to gain unusual regio- or stereo-control.
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Key Findings |
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Potential use in non-academic contexts |
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Impacts |
Description |
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Summary |
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Date Materialised |
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Sectors submitted by the Researcher |
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Project URL: |
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Further Information: |
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Organisation Website: |
http://www.bris.ac.uk |