Investigations Into the Development of New Methodologies for Organic Electrochemistry

有机电化学新方法开发的研究

• 批准号: 2092473
• 金额: --
• 依托单位: CARDIFF UNIVERSITY
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2018
• 资助国家: 英国
• 起止时间: 2018 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2092473
• 关键词: Investigations; Into; Development; New; Methodologies

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.

有机电化学是最清洁的化学加工技术之一。如果使用得当，只需一个电子就可以引发一系列反应，从而形成复杂的分子。这种级联往往无法通过其他手段进入。事实证明，电化学具有提供改进的可持续性指标和环境可接受的合成序列的优异潜力，但其采用远未广泛。因此，其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，可以针对特定的单电子转移（氧化和还原），获得具有独特反应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强有力的合成方法，用于各种分子间和分子内键形成过程。然而，这些方法的缺点是通常需要化学计量的氧化剂，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，通过电化学氧化交叉偶联消除了对化学计量氧化剂的需要，从而推进了现有技术的发展，其中阴极处的析氢是唯一的副产物。作为这项研究计划的一部分，我们将开发一系列新的方法，从容易获得的起始原料合成双杂环。待靶向的杂环种类包括恶唑、吡唑、吡咯、喹喔啉和苯并恶嗪等。

项目成果

Ball-Milling-Enabled Reactivity of Manganese Metal*.

• DOI: 10.1002/anie.202108752
• 发表时间: 2021-10-18
• 期刊: Angewandte Chemie (International ed. in English)
• 作者: Nicholson WI;Howard JL;Magri G;Seastram AC;Khan A;Bolt RRA;Morrill LC;Richards E;Browne DL
• 通讯作者: Browne DL