Oxidation Of Olefins Catalyzed By AuCl And The Selective Ring-Opening Reaction Of Oxaziridine

The first part of this thesis is about the oxidation of olefins catalyzed by AuCl.By using AuCl as the catalyst, tert-butylhydroperoxide(TBHP) as the oxidation reagent, we realize the cleavage oxidation of aryl-substituted olefins. Ketones or aldehydes are formed in this reaction.It is the first example of the similar oxidation reactions catalyzed by homogeneous gold catalysts. This research provides a new understanding of the gold chemistry, and will broaden the application of gold catalysts in the organic synthesis.This reaction has a mild condition and a fairly well yield insofar as the aryl-substituted olefins are concerned, therefore it will be quite efficient in the transformations from olefins to ketones or aldehydes.The solvent of this reaction is water, which makes the work-up procedure quite simple. Furthermore, it is environmental benign and satisfies the requirements of Green Chemistry, therefore additionally broaden the scope of this reaction.The second part of this thesis is about the selective ring-open reaction of oxaziridine.The oxaziridine has a strained 3-member ring which contains three different bonds, N-O bond, N-C bond, and C-C bond. These bonds have different bond energies, therefore will be cleaved differently under different conditions.We developed a new methodology to selectively open the oxaziridine ring under differently conditions. By using the Lewis acid such as AgOTf as the catalyst, the C-O bond is cleaved and nitrone is formed. When Ac₂O was added to the above reaction system, the oxaziridine will be opened in another way, by the cleavage of the N-0 bond, and amide is formed.This reaction has a mild condition and a fairly well yield insofar as the 3-aryl-substituted oxaziridines are concerned. Since oxaziridines have a broad application in organic synthesis, for example, as the hetero atom transfer reagents, this selectively ring open of the oxaziridine will have more application. Furthermore, we found that the use of Ac₂O can change the reaction result dramatically. Although the reason is unclear, this research still has a great usefulness in synthetic chemistry.