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Details of Grant 

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:
Researcher Co-Investigators:
Project Partners:
Department: Chemistry
Organisation: University of Bristol
Scheme: Standard Research (Pre-FEC)
Starts: 06 March 2000 Ends: 05 July 2003 Value (£): 185,047
EPSRC Research Topic Classifications:
Catalysis & Applied Catalysis
EPSRC Industrial Sector Classifications:
Chemicals Pharmaceuticals and Biotechnology
No relevance to Underpinning Sectors
Related Grants:
Panel History:  
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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Organisation Website: http://www.bris.ac.uk