New Catalytic Strategies for Metal-Free C-C Bond Formation

无金属 C-C 键形成的新催化策略

• 批准号: 2108986
• 金额: --
• 依托单位: University of Bath
• 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-2108986
• 关键词: New; Catalytic; Strategies; Metal; Free

Transition metal-catalysed cross-coupling is a uniquely powerful tool for the formation of sp2-sp2 and sp2-sp3 C-C linkages. However, challenges inherent in sp3-sp3 couplings have largely impeded the development of generally applicable solutions to this problem. Moreover, a reliance on transition metal catalysts to forge alkyl-alkyl linkages can lead to problems in a drug development setting, as these catalysts are prone to poisoning by the basic functionalities commonly encountered in drug-like molecules. Additionally, trace metal contamination is a serious concern in a pharmaceutical manufacture. For these reasons, a metal-free approach to C(sp3)-C(sp3) bond formation could prove transformative in organic synthesis. In this project, we will explore a number of approaches to metal-free C(sp3)-C(sp3) bond formation without reliance on metal catalysis, using visible-light photocatalysis to generate radical intermediates. Our initial objective is to develop a novel, one-pot homologation process for alkyl carboxylic acids, extending an aliphatic chain by a single carbon. Such a process would be synthetically powerful, but is currently unachievable in a direct fashion.

过渡金属催化的交叉偶联是用于形成sp2-sp2和sp2-sp3 C-C键的独特有力的工具。然而，sp3-sp3偶联中固有的挑战在很大程度上阻碍了对该问题的普遍适用的解决方案的开发。此外，依赖于过渡金属催化剂来形成烷基-烷基键可能导致药物开发环境中的问题，因为这些催化剂易于被药物样分子中通常遇到的基本官能团中毒。此外，微量金属污染是制药中的一个严重问题。由于这些原因，C（sp3）-C（sp3）键形成的无金属方法可以证明在有机合成中具有变革性。在这个项目中，我们将探索一些方法来形成无金属的C（sp3）-C（sp3）键，而不依赖于金属催化，使用可见光催化剂产生自由基中间体。我们的初步目标是开发一种新的，一锅同系化过程的烷基羧酸，延长一个单一的碳脂肪链。这样一个过程将是综合强大的，但目前无法以直接的方式实现。