Intermolecular Hydroacylation: A New Reaction for Organic Synthesis

烯烃的氢酰化反应是基于C-H键活化的越来越多的转化的一个例子。这种转化有可能成为一种强大的合成工具；它由一些过渡金属催化剂推动，而且本质上是原子经济的。该反应的实用性受到关键的酰基金属中间体发生脱羰基化的倾向的限制，从而产生还原的底物和不活跃的催化剂。在这项建议中，我们详细介绍了一种新的分子间氢酰化反应方法，该方法利用了侧链杂原子的稳定能力，允许在温和的条件下使用低催化剂负载将烷基醛直接加成到一系列官能化的烯烃上。开发一个成功的体系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体选择性过程之前，将首先研究基本的反应性。还将研究在该工艺中直接使用酒精底物的方法。

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.