Novel approaches to metal free catalysis

本文提出的研究将探索硼结构，以开发创新的催化工艺，提供过渡金属（TM）催化剂无法获得的独特反应性，特别是在C-H官能化过程中。我们的长期目标是完善这方面的知识，以开发独特的催化概念，简化催化剂的开发，并以最低的成本为最终用户（学术和工业研究人员）提供催化工艺，同时遵守绿色化学的指导方针（无溶剂，无有毒副产物，简单合成）。 第一个主题将涉及发展转移硼基化反应进行C-H硼基化的烯烃和应用这种方法来产生有趣的化学图案。转移硼基化是我们研究小组开发的一种反应，包括使用一种消耗性芳基硼酸酯（Ar-B（OR）2）来硼化芳烃（Ar '-H），释放Ar-H和Ar'-B（OR）2。通过在催化过程中避免具有B-H键的物质，我们可以使使用传统催化剂（例如含有烯烃、炔或羰基部分的催化剂）难以硼化的底物硼化。我们还希望利用在溶液中两种不同的芳基硼酸酯之间观察到的平衡来设计活性硼酸酯试剂，当以亚化学计量的量使用时，该活性硼酸酯试剂将增加催化活性。在第二个主题中，我们将开发算法，这将允许一个组合的计算方法，挫败刘易斯对（FLP）化学和催化剂的发现。利用我们的知识，受挫刘易斯对催化剂和本地化-离域矩阵的计算设计，我们将确定不变量，将描述的电子和空间特性的FLP。我们将开发一种算法，该算法将使用由这些不变量组成的数据库，该不变量将预测刘易斯酸和刘易斯碱之间相互作用的性质，并快速预测可能的刘易斯对的FLP反应性。该方法将使用我们将在实验室进行的量热研究进行校准。 最后一个主题是在碳电极上协调FLP，以调节催化剂的电子性质，而不需要结构修饰。我们想证明电化学可以作为一种工具来帮助量化FLP的空间位阻并调节其反应性。我们将特别接枝C-H硼化催化剂，看看电子调制对催化的影响。我们还将开发一种电化学方法来量化FLP的空间特性。

The research proposed here will explore boron architectures to develop innovative catalytic processes that offer unique reactivity not accessible to transition metal (TM) catalysts, notably in C-H functionalization processes. Our long-term goal is to refine this knowledge to develop unique catalytic concepts that will simplify catalyst development and for catalytic processes that will be readily usable by end users (academic and industrial researchers) at a minimal cost, while respecting the guidelines of green chemistry (solvent-free, no toxic by-products, simple synthesis). The first theme will involve developing the transfer borylation reaction to carry out the C-H borylation of alkenes and apply this method to generate interesting chemical motifs. The transfer borylation, a reaction we developed in our research group, consists in using one expendable arylboronate (Ar-B(OR)2) to borylate an arene (Ar'-H), releasing Ar-H and Ar'-B(OR)2. By avoiding species with B-H bonds during catalysis, we can borylate substrates that are otherwise challenging to borylate using traditional catalysts, such as the ones containing alkene, alkyne or carbonyl moieties. We also want to exploit the equilibrium observed between two different arylboronates in solution to design active boronate reagents that would increase the catalytic activity when used in substoichiometric amounts. In the second theme, we will develop algorithms that will allow a combinatorial computational approach to frustrated Lewis pair (FLP) chemistry and catalysts' discovery. Using our knowledge on the computational design of frustrated Lewis pair catalysts and localization-delocalization matrices, we will determine invariants that will describe the electronic and steric properties of FLPs. We will develop an algorithm that will use a database made of these invariants that will predict the nature of the interaction between a Lewis acid and a Lewis base and quickly predict the FLP reactivity of possible Lewis pairs. This method will be calibrated using calorimetric studies that we will carry out in our laboratory. The last theme consists in coordinating FLPs on carbon electrodes to modulate the electronic properties of catalysts without requiring structural modifications. We want to demonstrate that electrochemistry can be a tool to help quantify the steric hindrance of FLPs and modulate their reactivity. We will notably graft C-H borylation catalysts to look at the effect of electronic modulation on catalysis. We will also develop an electrochemical approach to quantify the steric properties of FLPs.