This thesis describes two novel transformations (a method to synthesize alkylidene phthalides and a different approach toward the Baeyer-Villiger oxidation) and the development and mechanistic study of a metal-free oxidation of arenes.Chapter 1 introduces the concept of alkene oxyamination. Synthesis of a series of hydroxylamine derivatives of endocyclic peroxides was undertaken, which were then reacted with nitrogen, sulfur and carbon nucleophiles. This led to the discovery of a new reaction that provides access to alkylidene phthalides, a class of compounds which exhibit interesting biological activity.Chapter 2 describes the development of an alternative approach to the Baeyer-Villiger oxidation, through the reaction of hydrogen peroxide and a nitrile in the presence of a base.Chapter 3 describes direct methods for the formation of new aromatic C-O bonds, followed by the presentation of an organic peroxide mediated approach. Herein, an examination of the mechanism of the reaction of a malonoyl peroxide with an arene is studied through Hammett analysis, isotope labeling experiments, EPR studies, DFT calculations and reactivity patterns.Chapters 4 and 5 present the experimental procedures and analytical data relevant to the three reactions developed.Chapter 6 contains a bibliography.
|Date of Award||22 Aug 2016|
- University Of Strathclyde
|Sponsors||University of Strathclyde|
|Supervisor||Nick Tomkinson (Supervisor) & Allan Watson (Supervisor)|