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Details of Grant 

EPSRC Reference: GR/K71127/01
Title: THE DESIGN,SYNTHESIS,AND APPLICATION TO CATALYSIS OF CHIRAL N5-CYCLOPENTADIENYL COMPLEXES
Principal Investigator: Whitby, Professor RJ
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Zeneca
Department: Sch of Chemistry
Organisation: University of Southampton
Scheme: Standard Research (Pre-FEC)
Starts: 01 December 1995 Ends: 30 November 1998 Value (£): 162,159
EPSRC Research Topic Classifications:
Asymmetric Chemistry Catalysis & Applied Catalysis
EPSRC Industrial Sector Classifications:
Pharmaceuticals and Biotechnology
Related Grants:
Panel History:  
Summary on Grant Application Form
h5-Cyclopentadienyl transition metal complexes are used in many catalytic processes but there has been limited success in inducing asymmetry from a chiral cyclopentadienyl ligand to the products. For high enantioinductions we believe that the bound cyclopentadiene should posses planar chirality (i.e. be unsymmetrically substituted) and this must be induced from a chiral substituent to avoid the need for resolution. Developing methods for directing metallation of one enantioface of a cyclopentadiene provide our initial challenge. Steric hindrance from a favoured rotomer or fused ring, or direction from a co-ordinating group provide methods. The ligand must also redesigned to provide a steric block on one side of the complex and a roof on the other to ensure efficient asymmetric induction, but to otherwise minimise hindrance of the metal centre. This design makes the ligands equally applicable to mono- and di-cyclopentadienyl systems. A wide range (Cp) are proposed which fit this model and are readily synthesised from cheap homochiral starting materials. Applications include carbometallation of alkenes (CpCpZrCI2), reduction of imines, enamines, and alkenes (CpCpTiCI2,CpRu(CO)2), and hydroformylation of styrene (CpRh(CO)2).
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Organisation Website: http://www.soton.ac.uk