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Details of Grant 

EPSRC Reference: GR/M56937/01
Title: ELECTROCHEMICAL CONTROL OF CATALYTIC ASYMMETRIC SYNTHESIS USING REDOX-ACTIVE CHIRAL LIGANDS
Principal Investigator: Bryce, Professor M
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Department: Chemistry
Organisation: Durham, University of
Scheme: Standard Research (Pre-FEC)
Starts: 08 November 1999 Ends: 07 November 2001 Value (£): 101,971
EPSRC Research Topic Classifications:
Asymmetric Chemistry
EPSRC Industrial Sector Classifications:
No relevance to Underpinning Sectors
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Summary on Grant Application Form
We have very recently demonstrated that a chiral TTF-oxazoline and a chiral ferrocene-oxazoline ligand act as catalysts in palladium-based allylic substitution reactions. In situ electrochemical recycling of the ligand species has a dramatic effect on improving the efficiency of the reaction. We propose to explore this unprecedented effect using novel chiral ligands which contain a group at the reactive site which can be addressed electrochemically (viz. ferrocene, 1,3-dithiole) as chiral modifiers in organometallic reactions. Altering the potential in the electrolysis media should enable us to control the coordination of the metal to the ligand (and possibly the conformation of the ligand) thereby developing a catalytic system, which is under electrochemical control, for a range of asymmetric synthetic processes. The transformations we propose to explore are: (I) the synthesis of secondary alcohols, (ii) additions of carbon nucleophiles to C=C bonds, (iii) Diels-Alder reactions, (iv) Aldol reactions.
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