Exploration of novel paradigms in metal-free catalysis

无金属催化新范式的探索

• 批准号: RGPIN-2016-05886
• 负责人: Fontaine, FrédéricGeorges
• 金额: $ 5.46万
• 依托单位: Université Laval
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2020
• 资助国家: 加拿大
• 起止时间: 2020-01-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=710016
• 关键词: Exploration; novel; paradigms; metal; free

There has been great interest in the past few years in the design of novel and green technologies to replace catalytic systems that rely mainly on expensive and toxic noble metals. As such, most researchers have been focusing their work on using base metals rather than second- and third-row transition elements (rhodium, iridium, platinum, palladium). Another promising approach consists of using Frustrated Lewis Pair (FLPs), a popular concept termed by Douglas Stephan to explain the reactivity of Lewis pairs prevented from forming adducts by steric or geometric constraints, as metal-free catalysts. These species can provide cheap, green and non-toxic alternatives to current industrial technologies. Our 10-year experience in the synthesis and reactivity of ambiphilic molecules (molecules having both Lewis acid and Lewis basic moieties in the framework) allows us to have a unique look on metal-free catalysis. Based on some important results we reported recently in FLP catalysis and on our knowledge of organometallic catalysis, we propose three hypotheses that will guide the development of efficient metal-free catalysts. Our program involves using these paradigms, with the help of computational work, to design and synthesize FLPs with tailored Lewis acidity and basicity to use as catalyst in industrially-relevant applications. The transformations that we propose to investigate in this proposal are amongst the most useful in synthetic chemistry and in the pharmaceutical industry. It will include the reduction of carbonyl moieties to alcohols, the catalytic C-H bond functionalization of arenes and alkanes, and the hydroamination of alkynes. The demonstration of the concepts presented in this proposal will allow the community to use FLPs for many other catalytic processes and make this technology a viable replacement for transition metals in 2-electron transfer processes.

在过去的几年中，人们对新型和绿色技术的设计引起了极大的兴趣，以取代主要依赖昂贵和有毒的贵金属的催化系统。因此，大多数研究人员一直将工作重点放在使用碱金属而不是第二行和第三行元素上（Rhodium，Iridium，Platinum，Palladium）。另一种有前途的方法是使用沮丧的刘易斯对（FLP），这是道格拉斯·斯蒂芬（Douglas Stephan）称之为流行的概念，以解释刘易斯对的反应性，阻止了通过空间或几何约束形成加合物，作为无金属催化剂。这些物种可以为当前工业技术提供便宜，绿色和无毒的替代品。 我们在Ambiphilic分子的合成和反应性的10年经验（在框架中具有Lewis Acid和Lewis基本部分的分子）使我们能够对无金属催化具有独特的外观。基于我们最近在FLP催化中报告的一些重要结果以及根据有机金属催化的了解，我们提出了三个假设，这些假设将指导有效的无金属催化剂的发展。我们的计划涉及在计算工作的帮助下使用这些范式，以量身定制的刘易斯酸度和碱性设计和合成FLP，以用作与工业相关的应用中的催化剂。 我们建议在该提案中进行调查的转变是合成化学和制药行业中最有用的转变之一。它将包括将羰基部分减少到醇，催化C-H键功能化以及烷烃的功能以及炔烃的氢化功能。本提案中提出的概念的演示将使社区可以将FLP用于许多其他催化过程，并使该技术成为2电子转移过程中过渡金属的可行替代。