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Title: Studies on face selectivity in 1,7-electrocyclisation reactions of nitrile ylides
Author: Taylor, Philip G.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1996
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This work is concerned with the cyclisation reactions of α,β and γ,δ-unsaturated nitrole ylides which have a chiral substituent on the terminal carbon atom of the diene system. The objective was to develop a method for the synthesis of chiral benzazepines using known chiral auxiliaries. The first and major part was targeted on the development of a synthetic route to N-(o-alkenylbenzyl)-benzamides functionalised at the alkene terminus with amide groups linked to Oppolzer's sultam or Evan's oxazolidinone as chiral substituents. Several synthetic routes were explored but, although model compounds could be prepared, the target compounds remained elusive. The second part was concerned with similar compounds that had chiral ester rather than amide substituents. These proved easier to prepare and some preliminary work on the cyclisation of an achiral model system gave rise to some new chemistry involving the expected 1,7-electrocyclisation. This was followed by an unprecedented base catalysed migration to give a 5H-2-benzazepine. The occurrence of this migration led to a modification of the structure of the chiral target compounds and was followed by the preparation and cyclisation of two chiral esters that gave novel chiral cyclopropa[c]isoquinolines. In both cases the face selectivity shown was greater than observed in analogous intermolecular Diels-Alder reactions.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available