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Title: Chemoenzymatic oxidation of arenes : versatile intermediates for organic synthesis
Author: McIntyre , Peter Brian Alexander
Awarding Body: Queen's University Belfast
Current Institution: Queen's University Belfast
Date of Award: 2013
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Chapter 2 describes the chemoenzymatic synthesis of (-)epibatidine from a known cis-dihydrodiol. Crucia to the synthesis is a [3.3] sigmatropic rearrangement reaction. Two [3.3] sigmatropic rearrangements are described ; an allylazide rearrangement and an allylcyanate to isocyanate rearrangement. The synthesis was completed in eleven steps, yielding (~) -epibatidine in 21% yield. Chapter 3 describes the synthesis and characterisation of allytic cyetic sulphates from known cis~ tetrahydrodiols. These cyclic sulphates are ubiquitous synthetic intermediates, commonly used as electrophiles. Also described is the synthesis of a series of trans-1 ,2-chloro chlorosulphates. These compounds are by-products in the formation of cyclic sulphates and can be avoided by careful control of the reaction conditions. Chapter 4 describes the small-scale biotransformations of a series of substituted phenol metabolites, using the toluene dioxygenase (TOO) enzyme. The cyclohexenone cis-dial products are characterised fully and their absolute configurations are established using a variety of methods, including circular dichroism and stereochemical correlation. Pseudomonas putida UV4 and E.coli were used as sources of TOO for these reactions. Also described is the large-scale biotransformation of two of these phenols. The chemical synthesis of the cyclohexenone cis-diol products from known cistetrahydrodiols is also described as an alternative route to these compounds. Finally, the biotransformation of several substituted anilines using TOO is also described.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available