| EPSRC Reference: |
GR/L88870/01 |
| Title: |
NEIGHBOURING-GROUP EFFECTS OF ORGANOSULFUR SUBSTITUENTS IN FREE-RADICAL CHEMISTRY |
| Principal Investigator: |
Roberts, Professor B |
| Other Investigators: |
|
| Researcher Co-Investigators: |
|
| Project Partners: |
|
| Department: |
Chemistry |
| Organisation: |
UCL |
| Scheme: |
Standard Research (Pre-FEC) |
| Starts: |
01 October 1998 |
Ends: |
30 September 2001 |
Value (£): |
71,610
|
| EPSRC Research Topic Classifications: |
| Physical Organic Chemistry |
|
|
| EPSRC Industrial Sector Classifications: |
| No relevance to Underpinning Sectors |
|
|
| Related Grants: |
|
| Panel History: |
|
|
Summary on Grant Application Form |
|
We propose to use a physical-organic approach to investigate the chemistry of beta-alkylthioalkyl radicals in solution and then to make use of the knowledge obtained to develop methodology for C-C formation and for enantioselective reactions, which involve this type of radical as a key intermediate. EPR spectroscopy will be used to investigate the substituent effect of the beta-RS group on the rates of formation, structures, conformational preferences and rates of beta-scission of beta-alkylthioalkyl radicals. We predict that these radicals will exhibit pronounced nucleophilic properties. Carbon-centred radical addition to thioalkyl acrylates of the type H2C=C(CO2Et)CH2SR, to give initially beta-alkylthioalkyl radicals, will be exploited to provide new methods for C-C bond formation. The [3+2] annulation reactions between methylenecyclopropanes and alkenes, both electron-rich and electron-poor, to give methylenecyclopentanes is known to be catalysed by thiyl radicals. We propose to render this annulation reaction enantioselective by the use of homochiral thiyl radicals derived thermally or photochemically from homochiral disulfides. At all stages the EPR-based physical-organic approach will be used to inspire and guide the synthetic chemistry.
|
|
Key Findings |
|
This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk
|
|
Potential use in non-academic contexts |
|
This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk
|
|
Impacts |
|
| Description |
This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk |
| Summary |
|
| Date Materialised |
|
|
|
|
Sectors submitted by the Researcher |
|
This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk
|
| Project URL: |
|
| Further Information: |
|
| Organisation Website: |
|