Details of Grant 

EPSRC Reference:	GR/R66357/01
Title:	Bridgehead Enolates
Principal Investigator:	Simpkins, Professor NS
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department:	Sch of Chemistry
Organisation:	University of Nottingham
Scheme:	Standard Research (Pre-FEC)
Starts:	01 July 2002	Ends:	30 June 2005	Value (£):	174,013
EPSRC Research Topic Classifications:	Asymmetric Chemistry Chemical Synthetic Methodology
EPSRC Industrial Sector Classifications:	Chemicals Pharmaceuticals and Biotechnology No relevance to Underpinning Sectors
Related Grants:
Panel History:
Summary on Grant Application Form
It is commonly accepted amongst organic chemists that the Anti-Bredt nature of bridgehead enolates precludes their effective generation and use as reactive intermediates in organic synthesis. With the proposed work we are confident that we can completely re-write the rulebook as far as the generation of reactive bridgehead enolates (alpha-carbonyl organolithiums) is concerned. Preliminary results show that certain ketones and imides undergo effective enantioselective bridgehead substitution on treatment with chiral lithium amide bases. A key part of the proposed work is to explore the scope of this chemistry, especially in terms of establishing the types of carbonyl compounds, and range of bridge sizes, that can facilitate the bridgehead substitution. The synthesis of a range of compounds having small bridges (1-3 atoms) is proposed, followed by screening under a range of basic conditions. The scope of the asymmetric chemistry employing meso starting materials will also be established.Leading on from the above study, certain of the systems under examination may provide synthetic intermediates to natural products and their analogues. These aspects will be explored with the aim of illustrating the new approach in target synthesis. A key focus of this last phase of the work will be the synthesis of model compounds related to the biologically active welwitindolinone family and testing of the bridgehead metallation approach for installation of the bridgehead isothiocyanate function.
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Organisation Website:	http://www.nottingham.ac.uk