Self-assembly of asymmetric catalysts

不对称催化剂的自组装

• 批准号: EP/G036314/1
• 负责人: Matthew Clarke
• 金额: $ 44.11万
• 依托单位: University of St Andrews
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2009
• 资助国家: 英国
• 起止时间: 2009 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FG036314%2F1
• 关键词: Self; assembly; asymmetric; catalysts

Homogeneous catalysis plays an ever-increasing role in chemical synthesis. A catalyst allows the rate of a chemical reaction to be accelerated enormously, without the catalyst itself being used up in the reaction. The demand for chemical processes to be less harmful to the environment has increased the importance of reactions that utilise tiny amounts of catalyst to promote clean, efficient reactions between two chemicals that do not normally react with each other at a measurable rate. An important challenge in homogeneous catalysis is being able to control selectivity while retaining high catalytic activity. Many important drug and agro- chemicals exist as two mirror image structures called optical isomers that are related like your left and right hands, and despite sharing the same chemical composition, each mirror image has very different biological properties (New drugs that exist as optical isomers are now required to be prepared as a single optical isomer). There is therefore a massive research effort aimed at producing optically active compounds as single optical isomers for the pharmaceutical industry, with catalytic methods being potentially more efficient and less harmful to the environment. However, one of the big problems that prevents wider application of catalytic methods is the vast amount of time and money required to find the perfect catalyst for the specific reaction being studied. Many catalysts are difficult to make, and a catalyst that is good for one group of reactants is often hopeless for another. There is now massive interest in methodology that allows a large number of catalysts to be prepared rapidly. This programme has the ambitious aim of developing a new approach to solving this problem. The preparation of catalysts that can be changed by binding to a large collection of complementary additives in an instantaneous reaction that uses hydrogen bonding to hold the molecules together (Hydrogen bonds are the bonds that hold DNA together, and are formed very rapidly without any chemical reagents or intervention). If the project is fully successful, the time taken to find the perfect catalyst will be reduced dramatically, and chemists will have something analagous to a skeleton key for unlocking every door: a toolbox of catalysts that can be adjusted to every set of reactants that might be used. The project will involve detailed work on the mechanism of the self-asembly process, evaluating the strength of the hydrogen bonds and the conditions under which they are able to form. Using this approach some new development in currently challenging but important catalytic reactions should be possible

均相催化在化学合成中发挥着越来越重要的作用。催化剂可以大大加快化学反应的速度，而不会在反应中耗尽催化剂本身。对化学过程对环境危害更小的要求增加了利用微量催化剂促进两种通常不能以可测量的速率相互反应的化学物质之间的清洁，有效反应的重要性。均相催化的一个重要挑战是如何在保持高催化活性的同时控制选择性。许多重要的药物和农用化学物质以两种镜像结构存在，称为光学异构体，就像你的左手和右手一样，尽管具有相同的化学成分，但每个镜像具有非常不同的生物特性（以光学异构体存在的新药现在被要求制备成单一的光学异构体）。因此，有大量的研究工作旨在为制药工业生产光学活性化合物作为单一光学异构体，催化方法可能更有效，对环境的危害更小。然而，阻碍催化方法广泛应用的一个大问题是，为所研究的特定反应找到完美的催化剂需要大量的时间和金钱。许多催化剂很难制造，而且对一组反应物有用的催化剂对另一组反应物往往毫无作用。现在人们对能够快速制备大量催化剂的方法非常感兴趣。这个方案有一个雄心勃勃的目标，就是开发一种解决这个问题的新方法。利用氢键将分子结合在一起（氢键是将DNA结合在一起的键，在没有任何化学试剂或干预的情况下非常迅速地形成）的瞬间反应中，通过与大量互补添加剂结合来改变催化剂的制备。如果这个项目完全成功，寻找完美催化剂所需的时间将大大减少，化学家们将拥有一把打开每扇门的万能钥匙：一个催化剂工具箱，可以根据可能使用的每一组反应物进行调整。该项目将涉及对自组装过程机制的详细研究，评估氢键的强度以及它们能够形成的条件。利用这种方法，在目前具有挑战性但重要的催化反应中应该有一些新的发展

项目成果

Exploring the role of phosphorus substituents on the enantioselectivity of Ru-catalysed ketone hydrogenation using tridentate phosphine-diamine ligands

• DOI: 10.1039/c1cy00253h
• 发表时间: 2011-10
• 期刊: Catalysis Science & Technology
• 影响因子: 5
• 作者: S. Phillips;Kristian H. O. Andersson;N. Kann;Michael T Kuntz;P. Wawrzyniak;M. Clarke

The Stability of Imidazolidinones is the Primary Influence on the Catalytic Activity of Proline Amides and Proline Sulfonamides in Enamine Catalysis Using Alkyl Aldehyde Substrates

• DOI: 10.1002/ejoc.201201174
• 发表时间: 2013
• 期刊: European Journal of Organic Chemistry
• 影响因子: 2.8
• 作者: S. Tin;J. Fuentes;T. Lebl;M. Clarke