Palladium-catalysed alkene difunctionalisation in the synthesis of heterocycles

Smith, Craig D. (2016) Palladium-catalysed alkene difunctionalisation in the synthesis of heterocycles. PhD thesis, University of Glasgow.

Abstract

The opening chapter of this thesis is split in two with part one providing a summary of the existing methods for palladium-catalysed oxypalladation reactions resulting in the synthesis of oxygen containing heterocycles. Part two focuses on a niche area of palladium catalysis. Here, palladium-catalysed isohypsic reactions, in which the oxidation state of the palladium does not change throughout the entire catalytic cycle, are described and summarised.
Chapter 2 describes the extension of the heteroallylation reaction to incorporate the synthesis of lactones and the pursuit of an enantioselective oxyallylation reaction. The oxyallylation reaction in the synthesis of lactones was successfully applied to include five- and six- membered lactone rings in good yields, with the first enantioselective oxyallylation reaction being developed. Building upon this work, a copper-mediated oxyallylation reaction was developed. Additionally, a palladium-catalysed arylallylation reaction and C-H−cyclisation reaction were pursued.
Ensuing work, detailed in chapter 3, focused on the development of a novel isohypsic−redox sequence, combining both the palladium-catalysed isohypsic heteroallylation reaction with more traditional redox chemistry. The transformations developed give rise to the synthesis of heterocycles with complex functionality both quickly and efficiently using the one palladium source.

Experimental procedures and data are summarised in Chapter 4.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Palladium catalysis, alkene difunctionalisation, synthesis, heterocycles.
• Subjects: Q Science > QD Chemistry
• Colleges/Schools: College of Science and Engineering > School of Chemistry
• Supervisor's Name: France, Dr. David
• Date of Award: 2 December 2016
• Depositing User: Dr Craig Smith
• Unique ID: glathesis:2016-8003
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 09 Mar 2017 09:20
• Last Modified: 21 Apr 2017 07:46
• URI: https://theses.gla.ac.uk/id/eprint/8003