Synthesis and Reactions of Bridged Bicyclic Compounds

Young, Graham Andrew Reid (1971) Synthesis and Reactions of Bridged Bicyclic Compounds. PhD thesis, University of Glasgow.

Abstract

The research described in this thesis is devoted to synthetic and mechanistic studies in bridged bicyclic systems. The thesis is divided into three parts:- Part I: The Total Synthesis of Racemic Guaiol. The plant sesquiterpene guaiol has been synthesised in racemic form, from laevulinic acid and 2-methylcyclopentanon'e via an intermediate, l-methyltricyclo-(6,2,1,0 2,6)-undec-2 6-en-5,11-dione. Bridge fission of this diketone yields a hydroazulene enone-ester which has been elaborated to guaiol. Part II: The Acid Catalysed Cleavage of Bicyclo-(3,2,1)-oct-2-en-8-one. Although bicyclo-(3,2,1)-oct-2-en-8-one derivatives cleave in acidic solution to cycloheptene carboxylic acid derivatives, the corresponding alcohols do not fragment under similar circumstances. The corresponding syn alcohol undergoes a facile transannular cyclisation when treated with bromine. A similar transannular cyclisation occurs when the ketone is treated with bromine in an alcoholic solvent. Part III: A Re-investigation of the Reduction and Hydrolysis of Unsaturated Medium Ring Gem-Diesters. The previously reported base-catalysed transannular cyclisation of unsaturated medium ring gem-diesters has been re-investigated. In contrast to these earlier findings, the hydrolysis and reduction of these diesters proceed in the normal manner.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Organic chemistry
• Date of Award: 1971
• Depositing User: Enlighten Team
• Unique ID: glathesis:1971-78558
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 30 Jan 2020 15:10
• Last Modified: 30 Jan 2020 15:10
• URI: https://theses.gla.ac.uk/id/eprint/78558