铁催化的有机亲电试剂的羰基化反应研究

The use of iron salts as catalysts in chemistry has shown an exponential growth in the past years, and iron catalysts in carbonylation reaction also get some progress. Yet the substrate scope of carbonylation reaction by iron is narrow, most were focused on the amine and alkynes, for other types of carbonylation reaction reported less, still no breakthrough. Iron tended to go through single electron transfer, and can better with CO coordination. This project intends to design and synthesis of a series of iron catalyst, combining the two characteristics of iron catalyst, the iron as a medium to make free radicals and CO near more easily, to realize carbonylation reaction by iron catalysis under the more moderate conditions. In this project, we would from the three aspects: (1) Design, synthesis and characterization of iron catalysts; (2) Study the carbonylation of organic electrophilic reagents such as halogenated organic compounds, alkenes, alkynes, inert C-O, C-N bond by iron catalysis.(3) Study the mechanism of carbonylation reaction by iron catalysis.

铁催化的化学转化在过去的几十年中取得了巨大的进展，铁催化剂在羰基化反应中也有一定的应用。然而铁催化的羰基化反应大部分局限在炔烃与胺的反应上，对于其他类型的羰基化反应报道的较少，至今还没有突破性的进展。铁在催化化学转化时一般倾向发生单电子转移，同时又能较好的与CO配位。本项目拟设计合成一系列铁催化剂，结合铁催化剂的这两个特点，将铁作为一种媒介使自由基和CO更加容易的靠近，实现温和条件下铁催化的有机卤代物的羰基化反应。拟从三个方面入手：（1）铁催化剂的设计、合成以及表征；（2）发展铁催化的有机亲电试剂如有机卤代物、烯烃、炔烃、惰性C-O、C-N化学键的羰基化反应；（3）对铁催化的羰基化反应进行机理研究。

铁催化的化学转化在过去的几十年中取得了巨大的进展，铁催化剂在羰基化合物的合成与转化中也有一定的应用。有机硼化合物在化学领域是一种非常重要的试剂。本项目拟采用廉价过渡金属作为催化剂实现了苯胺类化合物的双羰基化反应以及羰基化合物的脱氧硼化转化。主要完成了以下内容：（1）完成了以乙二醛为双羰基源的羰基化反应；（2）完成了铜催化的醛、酮类化合物的脱氧转化成偕二硼、偕硅硼以及苄基单硼类化合物，并通过同位素标记实验、手性转化以及结合计算的方法详细研究了该类反应；（3）完成了铁催化酮的脱氧转化成偕二硼类化合物；（4）完成了铁催化的酯类化合物的脱氧氢硼化转化成偕二硼化合物；（5）完成了铁/钌接力催化的醇的a-C-H键的硼化转化。在该项目执行期间，积极开展工作，顺利完成了该项目。