| EPSRC Reference: |
GR/R36497/01 |
| Title: |
Radical-Chain Redox Reactions Using Thiols as Polarity-Reversal Catalysts. |
| Principal Investigator: |
Roberts, Professor B |
| Other Investigators: |
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| Researcher Co-Investigators: |
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| Project Partners: |
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| Department: |
Structural Molecular Biology |
| Organisation: |
UCL |
| Scheme: |
Standard Research (Pre-FEC) |
| Starts: |
26 November 2001 |
Ends: |
25 November 2003 |
Value (£): |
115,541
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| EPSRC Research Topic Classifications: |
| Carbohydrate Chemistry |
Chemical Synthetic Methodology |
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| EPSRC Industrial Sector Classifications: |
| Chemicals |
Pharmaceuticals and Biotechnology |
| No relevance to Underpinning Sectors |
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Summary on Grant Application Form |
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We propose to build upon our successful preliminary studies of the thiol-catalysed redox rearrangement of benzylidene acetals, to explore the scope of this type of reaction and to apply it to systems of synthetic interest, especially in the area of carbohydrate chemistry. Functional-group compatibility a the possibility of sequential redox opening of two benzylidene acetal groups in the same molecule will be investigated. Applications of the method for regioselective deoxygenation of carbohydrates, including aminoglycosides, will be explored. The dependence of regiochemistry on stereoelectronic a polar factors will be studied and the results, supported by theoretical calculations, will be used to establish rules for the prediction of the regiochemical outcome. Substituted-arylidene and alkylidene acetals will be examined to determine the best type of substrate for the reaction. The radical-chain ring opening reaction will be compared with the known heterolytic opening induced by treatment of benzylidene acetals with N-bromosuccinimide. This methodology will be extended to develop thiol-catalysed redox cleavage of diarylmethyl ethers derived from primary, secondary and tertiary alcohols. Enantioselective deoxygenation of alcohols that yield prochiral C-centred radicals will be sought using homochiral thiols as polarity-reversal catalysts. The C-centred radicals produced from the acetals and ethers will be elaborated by their addition to co-reactants, such as alkenes and oxime ethers, tc provide non-metallic alternatives to radical sources such as RBr or RSePh + tin hydride in synthetic transformations.
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Key Findings |
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Potential use in non-academic contexts |
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Impacts |
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| Description |
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| Summary |
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Sectors submitted by the Researcher |
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