Development of electrosynthetic methods for the functionalisation of tertiary amides

Kaur, Mandeep (2016) Development of electrosynthetic methods for the functionalisation of tertiary amides. Masters by Research thesis (MSc), Manchester Metropolitan University.

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Abstract

Electrosynthesis is the formation of an organic molecule through the application of a potential across the surface of an electrode. There are numerous factors that make electrosynthesis an appealing method of synthesising and manipulating organic compounds, these include the ability to carry out a reaction at room temperature without additional chemical reagents. Importantly, electrosynthesis is considered one of the green chemistry technologies of the future. The aim of this project is to investigate how electrosynthesis can be applied and understood in the functionalisation of amides using the Shono-type oxidation. Amides are abundant in nature, and are of importance to the development of pharmaceuticals, being present in biological systems such as proteins and peptides. This thesis explores at how to generate a new C-X bond from a C-H bond (where X can be carbon or a heteroatom) adjacent to the nitrogen of an amide or carbamate by using “traceless electrons”. C-H bonds are inherently unreactive and this method, when fully understood, will be a powerful way to selectively functionalise organic molecules. To achieve this goal, new electrode materials have been investigated including the characterisation of reticulated vitreous carbon electrodes and pencil drawn electrodes in electrosynthesis. Several techniques have been employed such as cyclic voltammetry and scanning electron microscopy to understand the electroanalytical properties and characterisation of the electrodes. Both galvanostatic and potentiostatic methods will be used for the electrosynthetic C-H activation of the amides using a selection of electrolytes and conditions. The sustainable electrosynthetic functionalisation of these fundamental organic molecules will enable the chemistry community to apply electrosynthesis more widely.