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

烯烃和炔烃的氢酰化反应从根本上说是一个简单的过程，涉及到醛与烯烃或炔烃的加成以生成酮产品。虽然已知有许多金属催化剂可以促进反应，但这些体系中的大多数都效率低下，需要苛刻的反应条件，底物范围有限。这项提议的目的是开发新的催化剂系统，使该过程能够使用稳定、易于操作的络合物在温和的条件下操作，并在广泛的有机底物中发挥作用，从而高产率地提供产品。为了达到这一点，我们提出了一个包括有机化学家和无机化学家在内的合作研究计划。我们将设计新的配体和催化剂，以稳定关键的活性金属中心，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。随着催化剂的设计，我们将使用各种表征方法来研究该过程的机理，并将建立对反应的各个步骤的详细了解。然后，这些机械信息将被送入催化剂设计循环，以提供更有效的催化剂。该化学的应用包括有效地合成酮和烯酮体系，环合反应生成环酮，以及该化学在合成新的聚合物材料方面的潜在应用。

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.