Investigations Into the Development of New Methodologies for Organic Electrochemistry

有机电化学是最清洁的化学处理技术之一。如果运用得当，只需一个电子就可以启动导致复杂分子形成的反应级联。这样的级联通常不能通过其他方式获得。事实证明，电化学在提供更好的可持续性度量和环境可接受的合成序列方面具有极好的潜力，但它的采用还远远没有广泛。因此，它作为一种获取有用化学实体的技术的应用范围尚未完全实现。通过仔细调整电化学参数，可以有针对性地进行特定的单电子转移(氧化和还原)，获得具有独特反应活性和化学选择性的强大自由基中间体。脱氢交叉偶联是一种有效的合成方法，可用于各种分子间和分子内键的形成。然而，这些方法的一个缺点是对化学计量氧化剂的共同要求，这降低了原子经济性并产生需要分离的废物。这为电化学提供了一个令人兴奋的机会，通过消除化学计量比氧化剂的需要，通过电化学氧化交叉耦合，在阴极放氢是唯一的副产品，从而提高现有的技术水平。作为这项研究计划的一部分，我们将开发一系列从容易获得的原料合成脱氢杂环的新方法。作为目标的杂环类包括恶唑、吡唑、吡咯、喹恶啉和苯并恶嗪等。

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.