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Details of Grant 

EPSRC Reference: GR/L31258/01
Title: NEW APPROACHES FOR THE FORMATION OF C-C AND C-N BONDS USING FREE-RADICAL REACTIONS
Principal Investigator: Roberts, Professor B
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Department: Chemistry
Organisation: UCL
Scheme: Standard Research (Pre-FEC)
Starts: 01 December 1996 Ends: 30 November 1999 Value (£): 160,130
EPSRC Research Topic Classifications:
Chemical Synthetic Methodology
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Summary on Grant Application Form
The aims of the proposed research are to develop new methods for the formation of C-C and C-N bonds using free-radical chemistry. Three complimentary approaches will be investigated.1. The application of the concept of polarity-reversal catalysis of hydrogen-atom transfer reactions to inter- and intra-molecular hydroacylation reactions of aldehydes. This will involve the use of thiols as catalysts to promote the radical-chain addition of aldehydes to carbon-carbon multiple bonds. The synthesis of optically active adducts by the use of chiral thiols, chiral Lewis acids and chiral auxiliaries will be explored.2. The use of Lewis acids to complex unsaturated radical acceptors will be investigated as a means to control the polar character of these species. By complexation, electron-rich alkenes will be converted reversibly into electron-deficient acceptors, thus rendering them more susceptible to attack by nucleophilic radicals. This concept will be applied to both inter- and intra-molecular (rearrangement) processes and chiral Lewis acids will be investigated as a means to make these reactions enantioselective.3. Radical addition to carbenoids and to nitrenoids will be investigated. Carbon radical addition to stabilised sulfur and phosphorus ylides will be studied, as well as addition to transition-metal carbenes (eg Fischer and Shrock complexes).
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