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Title: The scope and limitation of the [1,2]- and [1,4]- RS shifts
Author: Eames, J.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 1997
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This thesis describes a variety of ways to synthesise substituted thiolanes (like A) and tetrahydrofurans (like B). We comment on the possible methods of activation of diol C, to promote either [1,2]- or [1,4]-SR migration to give either A or B. We discuss the effect of chain length, stereochemistry and structural variation at the migratory origin, terminus (including ring size) and the migrating substituent on the possible modes of ring closure. (Fig. 10231A) We also discuss the merits of the capture of the episulfonium ion G with a second sulfur atom (F; X=S) to give cyclic sulfides (e.g. I) and highlight the surprising difference between of an SH and OH towards an episulfonium ion. Furthermore, we comment on the kinetic and thermodynamic products of cyclisation. (Fig. 10231B) We also disclose new methods to synthesise a variety of substituted oxetanes, 1,2-oxathianes, disulfides and homochiral tetrahydrofurans and comment on the NMR features of these compounds.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available