Multicomponent Photocatalytic a-Tertiary Amine Synthesis

多组分光催化α-叔胺合成

• 批准号: 2276993
• 金额: --
• 依托单位: University of Cambridge
• 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-2276993
• 关键词: Multicomponent; Photocatalytic; Tertiary; Amine; Synthesis

Year 1: Generic training activities for all first-year student members of the CDT.Year 2-4: This project investigates the development of a multicomponent protocol to access a-tertiary amines in protected form from abundant chemical feedstocks, using visible light mediated photoredox catalysis. The optimised reaction conditions consistently form the model product in 91% assay yield, and the desired N-primary a-tertiary amines are easily accessed from the a-tertiary imine reaction products by hydrolysis or hydrogenation. The scope in both ketone and alkene components will be studied, in addition to the reaction mechanism. Towards elucidation of the reaction mechanism, key reaction intermediates will be isolated, enabling investigation of their reactivity, photochemical and photophysical properties. Discussion of the reaction mechanism will be backed up by computational analysis. Although the mechanistic data collected to date are inconclusive, a number of hypotheses have been ruled out, providing a good starting point for future mechanistic studies.

第一年：CDT所有一年级学生成员的一般培训活动。第2-4年：该项目研究开发一种多组分协议，使用可见光介导的光氧化还原催化，以保护形式从丰富的化学原料中获得α-叔胺。优化的反应条件始终以91%的测定产率形成模型产物，并且通过水解或氢化容易地从α-叔亚胺反应产物获得所需的N-伯α-叔胺。除了反应机理外，还将研究酮和烯烃组分的范围。为了阐明反应机理，将分离出关键的反应中间体，从而能够研究它们的反应性、光化学和光物理性质。对反应机理的讨论将得到计算分析的支持。虽然迄今为止收集的机理数据是不确定的，一些假设已被排除，为未来的机理研究提供了一个很好的起点。

项目成果

Thiol-Mediated a-Amino Radical Formation via Visible-Light-Activated Ion-Pair Charge-Transfer Complexes

通过可见光激活离子对电荷转移复合物形成硫醇介导的α-氨基自由基

• DOI: 10.17863/cam.78129
• 发表时间: 2021
• 作者: Kohara K