Novel Electrochemical syntheses of important heterocyclic scaffolds

重要杂环支架的新型电化学合成

• 批准号: 2754568
• 金额: --
• 依托单位: University of Surrey
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2022
• 资助国家: 英国
• 起止时间: 2022 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2754568
• 关键词: Novel; Electrochemical; syntheses; important; heterocyclic

Recent years have seen a burgeoning in novel methods for chemical activation, including organocatalysis, photoredox catalysis, methods for C-C bond coupling and various -bond insertion reactions, such as C-H activation. These relatively few 'catalysis activation concepts' have resulted in many powerful reactions. However, there is still considerable need for new modes of small molecule activation, and particularly asymmetric versions. This project proposes to address this issue by examining a novel method of -bond activation, namely electrochemical C-H activation. Electrochemistry is often seen as being an unfashionable 'black art', a view which completely disregards its huge industrial importance. According to the Electrochemical Encyclopaedia, there are currently 31 large scale industrial organic processes which involve electrochemistry in the key step. Further, electrochemistry has always been a significant but perhaps hidden tool for the lab synthetic chemist and synthetic organic electrochemistry has been rapidly disappearing from the UK chemistry community.The overall aim of the project is to build on our preliminary results combining electrochemistry, radical chemistry and flow chemistry and apply these techniques to the green and sustainable synthesis of a variety of novel heterocycle scaffolds. In particular, we shall look to develop electrochemical versions of the Prins and aza-Prins cyclisations using preliminary results obtained using our carboxylic acid or hemioxalate chemistry electrochemical route to radical generation, followed by electrochemical oxidation to form an oxonium ion to generate tetrahydropyrans, tetrahydrofurans, tetrahydropyridines and piperidines. We will investigate incorporating diversity into the products through the judicial introduction of substitutents in the starting materials and also via the variety of nucleophiles that may be trapped at the termination of the reaction (including halides, azide, oxygen and nitrogen nucleophiles, a Ritter reaction or a Friedel-Crafts reaction). Finally the products will be further utilised in developing electrochemical spirocyclisations to generate spiroketals.

近年来，化学活化的新方法迅速兴起，包括有机催化、光氧化还原催化、C-C 键偶联方法和各种键插入反应（例如 C-H 活化）。这些相对较少的“催化激活概念”导致了许多强大的反应。然而，仍然非常需要新的小分子激活模式，特别是不对称模式。该项目建议通过研究一种新的-键活化方法（即电化学 C-H 活化）来解决这个问题。电化学常常被视为一种不流行的“黑术”，这种观点完全忽视了其巨大的工业重要性。据电化学百科全书介绍，目前有31个大型工业有机过程的关键步骤涉及电化学。此外，电化学一直是实验室合成化学家的重要但可能是隐藏的工具，合成有机电化学已从英国化学界迅速消失。该项目的总体目标是在我们结合电化学、自由基化学和流动化学的初步成果的基础上，并将这些技术应用于各种新型杂环支架的绿色和可持续合成。特别是，我们将利用我们的羧酸或半草酸盐化学电化学途径产生自由基的初步结果，寻求开发Prins和氮杂Prins环化的电化学版本，然后通过电化学氧化形成氧鎓离子，生成四氢吡喃、四氢呋喃、四氢吡啶和哌啶。我们将通过在起始材料中合法引入取代基以及通过反应终止时可能被捕获的各种亲核试剂（包括卤化物、叠氮化物、氧和氮亲核试剂、里特反应或弗里德尔-克来福特反应）来研究将多样性纳入产品中。最后，这些产品将进一步用于开发电化学螺环化反应以生成螺缩酮。