Carbonyl reduction is a fundamental transformation that underpins synthetic chemistry. The re-routing of carbonyl reduction through less-conventional intermediates allows new selectivity and reactivity to be found in the resulting reaction space. We have shown for the first time that the unusual radical anions formed by electron transfer to the ester carbonyl group can be exploited in additions to alkenes. We have demonstrated that the reductive cyclisations of lactones, triggered by electron-transfer from SmI2-H2O, allow for highly decorated cyclopentane and cycloheptane ring systems to be constructed. Futhermore, the reductive cyclisations of lactones can be exploited in cyclisation cascades. The cascade sequences involve the generation and trapping of unusual radical anions formed from the ester carbonyl followed by the trapping of more conventional radical anions from the carbonyl groups of ketone intermediates.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:564309 |
| Date | January 2012 |
| Creators | Parmar, Dixit |
| Contributors | Procter, David |
| Publisher | University of Manchester |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | https://www.research.manchester.ac.uk/portal/en/theses/reductive-cyclisations-of-lactones-using-smi2-and-h2o(533c0430-fd14-4a24-93f2-18a7fb27232f).html |
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