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Title: Aziridinations of tethered allenes
Author: Feast, George C.
ISNI:       0000 0004 2725 8335
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2011
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This thesis describes the synthesis and reactivity of previously unprecedented bicyclic methylene aziridines via rhodium(II) catalysed cyclisation of α-allenic N-tosyloxycarbamates. These aziridines undergo reaction with organocuprates to give cis- disubstituted oxazolidinones by nucleophillic attack at the vinylic centre; plausible mechanisms for this process are discussed. Similar rhodium(II) catalysed cyclisations of β-allenic sulfamates afford cyclic enamines, aminocyclopropanes or bicyclic methylene aziridines; the product ratio depends on the allene substitution pattern. Suitably-designed substrates undergo trapping of the proposed intermediate amino allyl cation by internal nucleophiles or by cycloaddition. Finally, thermally-induced intramolecular cycloadditions of γ-allenic azides are described that give triazolines or [1,2,3]-triazoles.
Supervisor: Robertson, Jeremy ; Page, Lee W. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Organic chemistry ; Organic synthesis ; Physical Sciences ; Chemistry & allied sciences ; Synthetic organic chemistry ; Organometallic Chemistry ; aziridines ; allenes ; rhodium ; carbamates ; sulfamates