Exploiting Chalcogen Bonding and Non-Covalent Interactions in Isochalcogenourea Catalysis: Catalyst Preparation, Mechanistic Studies and Applications

合成操作和制备具有特定定制特性的特定分子结构的能力是合成化学的主要目标，其应用范围涵盖从材料化学到化学生物学的当代科学的广度。催化为社会提供了有效的工业过程，最大限度地减少能源消耗，废物产生和有害副产品的形成。该研究计划旨在通过开发一系列有效的催化剂并了解其基本特性，将这两个领域结合起来。开发的催化剂将用于发现新的有效途径，以制备高价值（手性）材料，这些材料将引起全球合成界以及制药和农用化学品行业的兴趣。该提案旨在从根本上了解一类特殊的简单有机分子（称为异硫属元素）如何能够催化广泛的选择性化学转化。通过了解特定过程中的每一步是如何工作的，以及通过理解催化剂结构的变化如何影响每一步的速率，我们希望揭示控制所形成的产物并最终导致更有效的反应过程的因素。有机材料作为催化剂的使用通常被归类为术语“有机催化”。这种方法的主要优点之一是，典型的转换可以在相对温和的，“绿色”的条件下进行，从而提供关键的可持续性效益。相比之下，使用金属的催化通常需要更严格的条件，包括严格排除水分和氧气以及使用通常昂贵的金属系统。然而，金属衍生的催化剂体系仍然大大优于有机催化类似物;在大多数有机催化反应中仍然需要高催化剂负载。因此，尽管有机催化方法具有明显的“绿色”优势，但迄今为止在工业环境中的吸收有限。在更广泛地使用有机催化方法之前，将需要催化剂效率的阶跃变化。对催化剂结构和产物之间的相互关系的更详细的机理理解对于支持未来的发展至关重要。这个建议将展示一个基本的定量理解的作用isochalcogenoureas催化。通过了解这些过程，我们将提供一系列催化剂，这些催化剂可以在非常低的浓度下使用，以允许合成化学和制药行业所需的各种支架。

The ability to synthetically manipulate and prepare specific molecular structures with defined bespoke properties is the main goal of synthetic chemistry, with applications that span the breadth of contemporary science ranging from materials chemistry to chemical biology. Catalysis provides society with efficient industrial processes that minimize energy consumption, waste production and the formation of harmful by-products. This research proposal aims to bring together these two areas, through developing a range of effective catalysts and generating an understanding of their fundamental properties. The developed catalysts will be used to uncover new and effective routes to prepare high value (chiral) materials that will be of interest to the global synthetic community as well as the pharmaceutical and agrochemical industries. This proposal aims to generate a fundamental understanding of how a particular class of simple organic molecule, known as an isochalcogenourea, is able to catalyze a wide range of selective chemical transformations. Through developing an understanding of how each step in a particular process works, and by comprehending how the rate of each step if effected by a change in catalyst structure, we hope to reveal the factors that provide control in the products formed and ultimately lead to more effective reaction processes.The use of organic materials as catalysts is often grouped under the term "organocatalysis". One of the main advantages of this approach is that typical transformations may be performed under relatively mild, 'greener' conditions, thus offering key sustainability benefits. By contrast, catalysis using metals usually requires more stringent conditions, including the rigorous exclusion of moisture and oxygen as well as the use of typically expensive metal systems. However, metal-derived catalyst systems still substantially outperform organocatalytic analogues; with high catalyst loadings still necessary in the majority of organocatalytic reactions. As a result, there has been limited uptake to date of organocatalytic approaches in industrial settings despite the clear 'green' advantages. A step change in catalyst efficiency will be required before the broader usage of organocatalytic approaches occurs. A more detailed mechanistic understanding of the inter-relation between catalyst structure and product is essential to underpin future developments. This proposal will demonstrate a fundamental quantitative understanding of the roles of isochalcogenoureas in catalysis. Through understanding these processes we will deliver a series of catalysts that can be used at very low concentration to allow synthetic access to the broad range of scaffolds required by the chemical and pharmaceutical industries.