Light-Activated Approaches to Highly Challenging Organic Electron Transfer Reactions

高挑战性有机电子转移反应的光激活方法

• 批准号: EP/K033077/1
• 负责人: John Murphy
• 金额: $ 26.99万
• 依托单位: University of Strathclyde
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2013
• 资助国家: 英国
• 起止时间: 2013 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FK033077%2F1
• 关键词: Light; Activated; Approaches; Highly; Challenging

Reduction and oxidation are central to chemistry and biology and relate to the addition of electrons or the removal of electrons from substances. Until now, many important but difficult reductions have only been accomplished with very powerful metal reducing agents, like sodium, but we have recently discovered simple neutral organic compounds, composed exclusively of the plentiful elements carbon, hydrogen and nitrogen, that act as powerful reducing agents. In 2012, we found that these substances become even more powerful reducing agents when irradiated with ultra-violet light and are even able to donate electrons to benzene rings that contain no significant electron-withdrawing groups. We now propose to develop this approach to determine the scope of the chemistry, using visible light to trigger the reactions, rather than untraviolet light, and converting our transformations it into protocols that use our electron donors catalytically.We believe that the principal reactions that are currently undertaken by sodium dissolved in liquid ammonia can be undertaken by our reagents in organic solvent and irradiated with light. This will not only add economic benefit through use of catalytic processes, but also convenience and enhancements in safety through avoiding reactive species like sodium that are hazardous both to use and to transport.

还原和氧化是化学和生物学的核心，与物质中电子的添加或去除有关。到目前为止，许多重要但困难的还原都是用非常强效的金属还原剂完成的，比如钠。但我们最近发现了简单的中性有机化合物，它们完全由丰富的碳、氢和氮元素组成，起着强效还原剂的作用。2012年，我们发现这些物质在紫外线照射下变得更强，甚至可以给苯环提供电子，而苯环中没有明显的吸电子基团。我们现在建议发展这种方法来确定化学的范围，使用可见光来触发反应，而不是紫外光，并将我们的转化转化为使用我们的电子供体催化的协议。我们相信，目前由溶解在液氨中的钠进行的主要反应可以用我们的试剂在有机溶剂中进行，并用光照射。这不仅可以通过使用催化过程增加经济效益，还可以通过避免使用和运输危险的反应性物质（如钠）来方便和增强安全性。

项目成果

Pushing the limits of neutral organic electron donors: a tetra(iminophosphorano)-substituted bispyridinylidene.

• DOI: 10.1002/anie.201505378
• 发表时间: 2015-09-14
• 期刊: Angewandte Chemie (International ed. in English)
• 作者: Hanson SS;Doni E;Traboulsee KT;Coulthard G;Murphy JA;Dyker CA
• 通讯作者: Dyker CA

Pushing the Limits of Neutral Organic Electron Donors: A Tetra(iminophosphorano)-Substituted Bispyridinylidene

突破中性有机电子供体的极限：四（亚氨基正膦）取代的双吡啶基

• DOI: 10.1002/ange.201505378
• 发表时间: 2015
• 期刊: Angewandte Chemie
• 作者: Hanson S

Predicting the reducing power of organic super electron donors

• DOI: 10.1039/c5ra26483a
• 发表时间: 2016-01-01
• 期刊: RSC ADVANCES
• 影响因子: 3.9
• 作者: Anderson, Greg M.;Cameron, Iain;Tuttle, Tell
• 通讯作者: Tuttle, Tell

Overturning established chemoselectivities: selective reduction of arenes over malonates and cyanoacetates by photoactivated organic electron donors.

• DOI: 10.1021/ja4050168
• 发表时间: 2013-07-31
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Doni, Eswararao;Mondal, Bhaskar;O'Sullivan, Steven;Tuttle, Tell;Murphy, John A.
• 通讯作者: Murphy, John A.

Proton transfer reactions of a bridged bis -propyl bis -imidazolium salt

桥联双丙基双咪唑鎓盐的质子转移反应

• DOI: 10.1002/poc.3567
• 发表时间: 2016
• 期刊: Journal of Physical Organic Chemistry
• 影响因子: 1.8
• 作者: Massey R