Intermolecular Hydroacylation: A New Reaction for Organic Synthesis

烯烃的氢酰化反应是基于碳氢键活化的越来越多的转化的一个例子。这种转变有可能成为一种强大的综合工具；它由许多过渡金属催化剂促进，具有固有的原子经济性。关键的酰基金属中间体倾向于进行脱碳，产生还原底物和无活性催化剂，限制了反应的效用。在这个提议中，我们详细介绍了一种利用悬垂杂原子的稳定能力进行分子间氢化的新方法，允许在温和条件下使用低催化剂负载将烷基醛直接添加到一系列功能化烯烃上。开发成功系统的关键是形成螯合稳定的酰基金属中间体。在研究非对映选择性和对映选择性过程之前，将首先研究基本反应性。本文还将探讨在该工艺中直接使用醇底物的方法。

The hydroacylation of alkenes is an example of a growing number of transformations based on C-H bond activation. The transformation has the potential to be a powerful synthetic tool; it is promoted by a number of transition metal catalysts and is inherently atom-economic. The utility of the reaction is limited by the propensity of the key acyl-metal intermediates to undergo decarbonylation, producing reduced substrates and inactive catalysts.In this proposal we detail a new approach to intermolecular hydroacylation utilizing the stabilizing ability of a pendent heteroatom to allow the direct addition of alkyl aldehydes to a range of functionalised alkenes under mild conditions using low catalyst loadings. The key to developing a successful system is the formation of chelation stabilised acyl-metal intermediates. The basic reactivity will initially be studied, before investigations into diastereoselective and enantioselective processes are undertaken. A method of employing alcohol substrates directly in the process will also be investigated.