'EPSRC/NSF Workshop Collaborative Proposal' Catalytic oxidative C-H bond functionalisation with high oxidation state N-heterocyclic carbene complexes

“EPSRC/NSF 研讨会合作提案”高氧化态 N-杂环卡宾配合物催化氧化 C-H 键功能化

基本信息

批准号：
EP/D058651/2
负责人：
Polly Arnold
金额：
--
依托单位：
University of Edinburgh
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2007
资助国家：
英国
起止时间：
2007 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FD058651%2F2
关键词：
EPSRC NSF Workshop Collaborative Proposal

项目摘要

Burning petrol and other hydrocarbons from fossil fuels is enormously damaging to the environment, and wasteful of these diminishing resources that should be used to make drugs, vitamins, and other important chemicals that improve the quality of life. However, the carbon-hydrogen bonds in these hydrocarbons are not only strong, but similar in strength, so selectively exchanging some of the hydrogens for the reactive groups that make the molecules into useful chemicals is difficult. Car catalytic converters use palladium particles to help fully oxidise the unburnt hydrocarbons in the exhaust, and protect us from petrol and carbon monoxide poisoning. The catalyst make the oxidation easier (they lower the energy barrier to the reaction).We have found that if you can dissolve the palladium in a solution (by surrounding each metal cation with binders, or ligands, to keep it solvated) it can be more selective, and pick up one hydrocarbon at a time, and thus also pick up another added reactive group. The moment the hydrocarbon becomes stuck to the palladium centre, it becomes much easier to remove one of its hydrogens, so it can be replaced with a useful, reactive group. Thus the solvated palladium compounds catalyse the formation of more complex compounds from simple hydrocarbons. We have made very selective ligands that stick more strongly to the palladium cations that any others, and make them even more reactive, but take up just enough space to make sure this reactivity is always highly selective for certain hydrogen atoms. This will help to make much more elaborate drug molecules, more selectively. Most importantly, the ligands help to stabilise the palladium in the middle of the combination step, when it is very electron deficient, and thus prone to damage. This will also allow a wider range of groups to be added. In the extreme, and most academically exciting palladium reactions, we plan to make stable molecules that mimic the most fragile intermediates in these reactive group additions, so we can study them in detail, and so that theoreticians can base calculations on the models to predict the future of palladium catalysis.So in the future we will need less palladium, and be able to make a wider range of complex drugs and pharmaceuticals from the simplest of fossil fuels, and biomass-derived organic compounds.

化石燃料中燃烧的汽油和其他碳氢化合物对环境造成了巨大破坏，并且浪费了这些减少的资源，这些资源应用于制造药物，维生素和其他改善生活质量的重要化学物质。然而，这些烃中的碳氢键不仅很强，而且强度相似，因此很难将某些氢汇聚为使分子成有用化学物质的反应性基团的某些氢凝胶非常困难。 CAR催化转化器使用钯颗粒来帮助完全氧化排气中未燃烧的碳氢化合物，并保护我们免受汽油和一氧化碳中毒的侵害。催化剂使氧化更容易（它们将能屏障降低到反应）。我们发现，如果您可以将钯溶解在溶液中（通过用粘合剂或配体环绕每种金属阳离子，以保持溶剂的溶剂溶解），它可以更具选择性，并一次捡起一个氢碳，从而添加了另一个氢碳。当碳氢化合物被粘在钯中心时，去除其中一种氢的时刻变得容易得多，因此可以用有用的反应性群代替。因此，溶剂化的钯化合物催化了简单碳氢化合物的更复杂化合物的形成。我们制作了非常有选择性的配体，这些配体更加强烈地粘在其他任何人的钯阳离子上，并使它们更具反应性，但要占用足够的空间，以确保这种反应性始终对某些氢原子具有很高的选择性。这将有助于更有选择地使更精致的药物分子。最重要的是，配体有助于在组合步骤中间稳定钯，因为它非常缺乏电子，因此容易损坏。这还将允许添加更广泛的组。在极端，最令人兴奋的钯反应中，我们计划制作稳定的分子，模仿这些反应性群体中最脆弱的中间体，以便我们可以详细研究它们，并可以在模型上基于计算基础，以便在模型上基于计算，以预测将来的钯的未来。化石燃料和生物质衍生的有机化合物。