Metal-free di-functionalisation of alkenes with malonoyl peroxides

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This thesis describes the development of reactions for the di-functionalisation of alkenes using a malonoyl peroxide. Chapter 1 examines the development of the an anti-oxyamination reaction of alkenes using a malonoyl peroxide. The investigation examines both the substrate scope of the process and explores further chemistry of the oxyaminated products to form heterocyclic derivatives. Chapter 2 describes the attempts to difunctionalised alkenes using a sulfur nucleophile and a malonoyl peroxide. The first successful new C-S bond formation used p-toluenesulfinic acid as the sulfur nucleophile which was accompanied by a 1,2-phenyl migration. This reaction mechanism was investigated to try to understand the formation of this unexpected product. Sulfonyl thioamide and acythioamide were investigated as alternative sulfur nucleophiles, however, the oxidation of the sulfur nucleophile by malonoyl peroxide was unavoidable. To probe the oxidation of the sulfur nucleophile, malonoyl peroxide was reacted with stilbene to form an orthoester which was then reacted with our sulfur nucleophile, providing insight into the mechanistic course of the process.

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