Delivering Hydroacylation as a General Reaction for Synthesis: A Combined Organic and Organometallic Approach

烯烃和炔烃的加氢酰化是一个基本上简单的过程，涉及醛与烯烃或炔烃的加成，生成含酮产物。尽管已知许多金属催化剂可以促进反应，但这些系统中的大多数效率低下，需要苛刻的反应条件并且底物范围有限。该提案的目的是开发新的催化剂系统，使该过程能够以高产率提供产品，使用稳定、易于处理的络合物，在温和的条件下运行，并且适用于多种有机底物。为了达到这一点，我们提出了一项涉及有机和无机化学家的合作研究计划。我们将设计新型配体和催化剂，使关键的活性金属中心稳定，同时仍允许反应进行。我们实验室的初步结果表明这种方法是有效的。除了催化剂设计之外，我们还将使用各种表征方法研究该过程的机理，并对反应的各个步骤建立详细的了解。然后，该机械信息将被输入催化剂设计循环中，以提供更有效的催化剂。所提出的化学应用包括酮和烯酮系统的有效合成、生成环酮的闭环反应以及该化学在新型聚合物材料合成中的潜在应用。

The hydroacylation of alkenes and alkynes is a fundamentally simple process involving the addition of an aldehyde across and alkene or an alkyne to generate a ketone-containing product. Although a number of metal catalysts are known to promote the reaction the majority of these systems are inefficient, require harsh reaction conditions and have limited substrate scope. The aim of this proposal is to develop new catalysts systems that will allow the process to deliver products in high yields, using stable, easy to handle complexes that operate under mild conditions, and that function for a wide range of organic substrates. To arrive at this point we propose a collaborative program of research involving both organic and inorganic chemists. We will design new classes of ligands and catalysts that allow stabilisation of the key reactive metal-centre while still allowing the reaction to proceed. Preliminary results from our laboratories have shown that such an approach is valid. Along with catalyst design we will study the mechanism of the process using a variety of characterisation methods, and will build up a detailed understanding of the individual steps of the reaction. This mechanistic information will then be fed into the catalysts design loop to deliver yet more effective catalysts. Applications of the proposed chemistry includes the efficient synthesis of ketone and enone systems, ring-closing reactions to generate cyclic ketones, and the potential application of the chemistry to the synthesis of new polymeric materials.