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)|