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

烯烃和炔烃的氢化酰基化基本上是一个简单的过程，包括在烯烃或炔烃之间加成醛以生成含酮的产物。虽然已知一些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，并且衬底范围有限。该提案的目的是开发新的催化剂系统，使用稳定、易于处理、在温和条件下操作的配合物，并对广泛的有机底物起作用，从而使该过程高产出产品。为了达到这一点，我们提出了一个涉及有机和无机化学家的合作研究计划。我们将设计新型的配体和催化剂，既能稳定关键的活性金属中心，又能使反应继续进行。我们实验室的初步结果表明，这种方法是有效的。随着催化剂的设计，我们将使用各种表征方法研究该过程的机理，并将建立对反应各个步骤的详细了解。然后，这些机械信息将被输入催化剂设计回路，以提供更有效的催化剂。提出的化学的应用包括酮和烯酮系统的有效合成，环闭合反应生成环酮，以及化学在合成新聚合物材料中的潜在应用。

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.