Investigations Into the Development of New Methodologies for Organic Electrochemistry

Organic electrochemistry represents one of the cleanest possible chemical processing technologies. When wielded appropriately, just a single electron is all that is needed to initiate a reaction cascade that can result in the formation of complex molecules. Such cascades cannot often be accessed by other means. It is proven that electrochemistry has excellent potential to provide improved sustainability metrics and environmentally acceptable synthetic sequences, yet its adoption is far from widespread. Consequently the breadth of its application as a technique to access useful chemical entities is yet to be fully realised. By careful tuning of electrochemical parameters, specific single electron transfers (oxidation and reduction) can be targeted, accessing powerful radical intermediates that have unique reactivity and chemoselectivity. Dehydrogenative cross coupling is a powerful synthetic approach for a variety of inter and intramolecular bond forming processes. However, a drawback of these methods is the common requirement for stoichiometric oxidants which reduces atom economy and generates waste products that require separation. This presents an exciting opportunity for electrochemistry to advance the existing state of the art by obviating the need for stoichiometric oxidants, through electrochemical oxidative cross coupling, with hydrogen evolution at the cathode the sole by product. As part of this research programme, we will develop a series of novel methods for dehydrogenative heterocycle synthesis from readily accessible starting materials. Classes of heterocycle to be targeted include oxazoles, pyrazoles, pyrroles, quinoxalines and benzoxazines, amongst others.