Novel arene transformations through nucleophilic dearomatization

通过亲核脱芳构化进行新型芳烃转化

• 批准号: 2239223
• 金额: --
• 依托单位: University of Liverpool
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2019
• 资助国家: 英国
• 起止时间: 2019 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2239223
• 关键词: Novel; arene; transformations; through; nucleophilic

This PhD program will focus on designing conceptually new synthetically useful arene functionalisations through ring expansion reactions and C-X bond activation. The first approach will be based on the cleavage of the aromatic ring C-C bonds as a key step. This step is notoriously challenging as it could not be conducted selectively even with the most active transition metal complexes. Recently, we successfully addressed this problem by applying a novel concept of metal-induced ring strain with iridium complexes (Angew. Chem. Int. Ed. 2017, 56, 3266; J. Am. Chem. Soc., 2019, 141 , 6048). In this project, we will take one step further and explore an alternative strategy for the aromatic C-C cleavage that will not require the use of transition metals. This strategy will rely on a selective dearomatisation using stable difunctional nucleophilic reagents and designer Lewis acids as a central concept. It would address the limitations of known ring expansion methods based on the application of highly reactive and unselective carbenes and nitrenes. The second approach will focus on novel photochemical functionalisations of aromatic C-H and C-Hal bonds using well-defined transition metal complexes and sensitising additives.During work on the project, the candidate will receive extensive training in organic and organometallic synthesis using Schlenk and glovebox techniques and will have hands-on experience in application of modern analytical methods (NMR, MS, GC/MS and HPLC). The knowledge and skills developed will provide the candidate with a solid foundation for his/her future academic or industrial career in organic chemistry and catalysis.

这个博士课程将专注于通过扩环反应和C-X键活化设计概念上新的合成有用的芳烃官能化。第一种方法将基于芳环C-C键的裂解作为关键步骤。这个步骤是众所周知的挑战，因为它不能选择性地进行，即使是最活跃的过渡金属络合物。最近，我们成功地解决了这个问题，通过应用一个新的概念，金属诱导环应变与铱配合物（Angew。Chem.Int.Ed.2017，56，3266; J. Am.化学会，2019，141，6048）。在这个项目中，我们将更进一步，探索一种不需要使用过渡金属的芳香族C-C裂解的替代策略。该策略将依赖于使用稳定的双官能亲核试剂和设计师刘易斯酸作为中心概念的选择性脱芳化。它将解决基于应用高反应性和非选择性卡宾和氮烯的已知扩环方法的局限性。第二种方法将专注于使用定义明确的过渡金属络合物和敏化添加剂对芳香族C-H和C-Hal键进行新型光化学官能化。在项目工作期间，候选人将接受使用Schlenk和手套箱技术进行有机和有机金属合成的广泛培训，并将拥有现代分析方法（NMR，MS，GC/MS和HPLC）应用的实践经验。所掌握的知识和技能将为候选人未来在有机化学和催化领域的学术或工业生涯奠定坚实的基础。