Organic Dications: Synthesis, Reactivity and Applications

有机双阳离子：合成、反应性和应用

• 批准号: EP/H02042X/1
• 负责人: John Murphy
• 金额: $ 54.03万
• 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: 2010
• 资助国家: 英国
• 起止时间: 2010 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FH02042X%2F1
• 关键词: Organic; Dications; Synthesis; Reactivity; Applications

One of the principal factors governing the reactivity of substances is their degree of electric charge - in simple terms, opposite charges attract, so the more charged a compound is, the more reactive it should be. Until now, the way to produce compounds that are highly electrophilic (very positively charged) was to use ''super-acids'', i.e. acids that are stronger than 100% sulfuric acid. Performing chemistry in super-acid has been very useful for understanding the reactions of super-electrophiles derived from hydrocarbons. This proposal addresses the preparation of novel and highly electrophilic species in molecules containing heteratoms (usually nitrogen) in organic solvents, and looks to study their reactivity. It has potential applications across a broad range of chemical reactions, and it could also have relevance to UK plc through taking first steps in the development of catalysts for performing reactions (like Friedel-Crafts reactions) that have traditionally used environmentally harmful reagents such as aluminium trichloride. Super-electrophile chemistry may also explain some of the biggest puzzles in bioorganic reaction mechanisms, involving reactions that are required for DNA synthesis (the formation of thymine derivatives from their uracil counterparts) and protein synthesis (preparation of methionine from homocysteine - methionine is the starting amino acid for all genes during translation). Even the mysterious but potentially very useful production of methane from carbon dioxide that is achieved by bacteria, could depend on the chemistry of the superelectrophiles that are discussed in this proposal.This is a new adventure in chemistry that we expect to have widespread applications.

控制物质反应性的主要因素之一是它们的电荷度--简单地说，相反的电荷相互吸引，所以化合物带的电荷越多，它的活性就越强。到目前为止，生产高度亲电(带正电)的化合物的方法是使用“超强酸”，即比100%硫酸更强的酸。在超强酸中进行化学研究，对于理解碳氢化合物衍生的超亲电分子的反应是非常有用的。这项建议致力于在有机溶剂中含有杂原子(通常是氮)的分子中制备新的和高度亲电的物种，并希望研究它们的反应性。它在广泛的化学反应中都有潜在的应用，它还可以通过在进行传统上使用环境有害试剂(如三氯化铝)的反应(如Friedel-Craft反应)的催化剂开发中的第一步，对UK plc具有相关性。超电泳化学还可以解释生物有机反应机制中的一些最大的谜题，涉及DNA合成(从尿嘧啶形成胸腺嘧啶衍生物)和蛋白质合成(从同型半胱氨酸制备蛋氨酸-蛋氨酸是所有基因在翻译过程中的起始氨基酸)所需的反应。即使是由细菌从二氧化碳中神秘但可能非常有用的甲烷产生，也可能取决于这一提议中讨论的超亲电体的化学。这是化学中的一项新冒险，我们预计将有广泛的应用。

项目成果

The third hydrogenase

• DOI: 10.1002/9783527664160.ch5
• 发表时间: 2014-08
• 作者: Callum Scullion;John A. Murphy

Superelectrophilic Amidine Dications: Dealkylation by Triflate Anion

超亲电脒二阳离子：三氟甲磺酸根阴离子脱烷基化

• DOI: 10.1002/anie.201202990
• 发表时间: 2012
• 期刊: Angewandte Chemie International Edition
• 作者: Kovacevic L