过渡金属催化的氢酰化反应研究

Transition metal catalyzed hydroacylation reactions are potentially powerful methods for the preparation of ketones. The reaction employs cheap and readily available aldehydes and alkenes or alkynes as starting materials, and is 100% atom-economic and thus can be considered "green". However, until now there is no general method for alkene and alkyne hydroacylation with non-chelating assisted aldehydes. The main challenge for this reaction is decarbonylation from the acayl metal hydride intermediate. By introducing an amino group into the new designed ligand, we expect to stabilize the acyl hydride intermediate which does not require a chelating substrate. A variety of ligands have been proposed, varying in backbone rigidity. Rhodium、cobalt and nickel complexes with these ligands will be tested for activity in hydroacylation reactions. The goal of this proposed research is to develop a practical catalytic system, as well as mechanistic insight for the general scenario of the hydroacylation reaction: the coupling of any alkene or alkyne with any aldehyde to give a ketone. By achieving this ambitious goal, hydroacylation can become a general and robust synthetic method for the production of fine and bulk chemicals, new materials and target molecules.

过渡金属催化的氢酰化反应是制备酮类化合物的有效方法之一。该反应使用相对易得的醛类与烯烃/炔烃为起始原料，具有100%原子经济性。然而，到目前为止还没有普遍有效的方法将不含有螯合基团底物进行加氢酰化反应。该反应的主要挑战是酰基金属氢基中间体易于发生去羰基化副反应。本项目提出设计合成含有胺基的配体用于稳定中间体，从而解决该反应只能应用于螯合底物的局限性问题。另外，通过改变配体骨架的柔韧性，申请人设计了一系列配体。该项目的目标是与机理研究相结合，拓展更加普遍，实用的催化体系——具有普遍性的醛类与烯烃/炔烃都能进行反应得到具有普遍性的酮类化合物。如果目标实现，加氢酰化反应将会成为在精细化工，新材料制备和目标分子合成中有强而有效的合成手段。

C-H键活化是有机化学科研工作者的最感兴趣研究方向之一；相比传统的官能团化方法，活化C-H键随后构建其他化学键，更加高效；经过几十年的研究，主要采用过渡金属催化、光催化、电化学等方法活化C-H键。该报告主要研究铑催化的杂环醛类的C-H键活化，通过氢酰化反应构建C-C键，制备酮类化合物。设计出2-吡啶乙醛和2-噻吩乙醛作为试验底物，使用目前报道的最佳的催化剂和配体组合对2-噻吩乙醛为底物的氢酰化反应进行了探索。同时，利用所设计合成配体，合成催化剂，进行了C-C、C-N偶联反应。对所得配合物，进行了光化学产氢和荧光探针方面的研究。