基于借氢方法的多相催化选择性合成烷基伯胺研究

Alkyl primary amines are a very important family of compounds in chemistry and biology. Herein, we wish to study the highly selective synthesis of primary amines directly from alcohols and ammonia promoted by the cerous phosphate supported ruthenium catalyst using borrowing hydrogen methodology in this project. A series of heterogeneous ruthenium catalysts will be synthesized by co-precipitation, co-impregnation, deposition-precipitation methods with high surface area cerous phosphate as the carrier, and then investigated for the reaction. Under the optimized reaction conditions, the substrate scope is to be further examined. Meanwhile, the relationship between the catalyst structure and the reaction conversion and selectivity, as well as the borrowing hydrogen mechanism of the heterogeneous ruthenium catalyst will be further discussed. A possible catalytic cycle is to be proposed. For the reaction, the only byproduct is water and there is no need for additional hydrogen source. Furthermore, the catalyst can be easily separated from the reaction mixture and reusable with high activity and selectivity. Hence, it is accord with the green chemistry and atom economy principle. This research will have important guiding significance for the further development of highly selective and green organic reactions.

在化学和生物学中，烷基伯胺是一类极其重要的化合物。本项目拟基于"借氢"策略，使用磷酸铈担载的钌作为多相催化剂，醇作为一种绿色烷基化试剂，氨水/氨气作为氮源，直接一步高效合成系列烷基伯胺化合物。具体从研制高比表面的磷酸铈/掺杂磷酸铈材料入手，结合共沉淀、共浸渍、沉积-沉淀技术，合成系列多相钌催化剂，利用微量反应测试其催化性能，建立最优反应条件，并进行底物适应性考察。同时，探索催化剂结构特征与反应转化率和选择性之间的关联，揭示多相钌催化剂"借氢"作用机制，提出一个合理的催化循环。此反应主要副产物是水，不需要外加氢源，所用催化剂和产物易于分离，可回收循环使用，符合绿色化学和原子经济性原则。这一研究对于进一步发展高选择性和环境相容性的有机合成新反应具有重要指导意义。

开发新型多相催化剂和发展有机化合物新的成键模式是当代绿色有机合成反应的关键科学问题。本项目基于均相催化剂多相化的策略，使用羟基磷灰石、阴离子树脂、氮掺杂炭材料作为载体，结合共沉淀、浸渍、离子交换、沉积-沉淀技术，制备了一系列多相Au、Pd、Co等催化剂，以醇作为一种绿色烷基化试剂，直接一步高效合成系列酰胺和不饱和酮化合物。同时，我们结合HRTEM、XRD、XPS等表征技术，建立了催化剂结构和反应转化率及选择性之间的关联，揭示了多相纳米催化反应机制。本项目开发的催化剂具有底物普适性好、循环稳定性高、易于同产物分离等特点，符合绿色化学和原子经济性原则。本项目为进一步发展高选择性和环境相容性的有机合成新反应建立了良好的工作基础。