均相/非均相Au,Pd催化酯的C-O键活化反应研究

Used a series of palladium(0), palladium(II) complexes and supported nano Au, Pd as catalysts, esters as environmentally benign and atom-economical carbon sources, homogeneous palladium catalyzed C-O bond activated reaction and heterogeneous catalyzed C-O bond activated reaction of the ester would be researched for achieve recyclable green catalysis reaction. Meanwhile, this project will comparative study the catalytic reaction mechanism of two kinds of systems and explore the foundamental law of Au, Pd catalyzed reaction by means of isolated reaction intermediates and tested the valence state changes of fresh and used catalysts. Many kinds of directed acyl C-O activated reaction of ester would be studied and realized. The metal catalyzed reaction of alkyl ester which containing sp3 C-O bond would be tried. In addition, the applied research of discovered novel reaction, for instance, the modification of cinchona alkaloid would be conducted. This project has important significance and value to the C-O activation reaction study, the deepen and extension of Au, Pd metal-organic chemistry and the development of ester's chemistry.

本课题拟采用一系列0价钯，2价钯配合物以及负载纳米Au,Pd做催化剂，利用酯作为环境友好，原子经济的碳源，研究均相Pd催化酯的C-O键活化反应以及非均相催化酯的C-O键活化反应，实现可循环的绿色催化反应。同时通过分离反应中间体、测定反应前后催化剂的价态变化等方法，对比研究两种体系的催化反应机理，探究Au,Pd催化反应的根本规律。研究并实现多种导向酯的酰基C-O键活化反应，并尝试含有Sp3 C-O键的烷基酯的金属催化反应。此外，利用已发现的新反应，进行应用性研究，如金鸡纳碱的改性。此项目对C-O键的活化反应研究，对Au,Pd金属有机化学的深入扩展以及酯化学的发展具有重要的意义和价值。

酯类在工业中大量生产，并作为最主要的溶剂使用。利用酯作为碳源可以得到对环境更加友好，原子经济性更高的反应，从而替代当前形成C-C键的反应中的卤化物、磺化物。本项目中，我们不仅发现了均相Pd催化的酯酰基C-O键活化反应，而且突破了非均相纳米Pd, Au催化的酯酰基C-O键活化反应，筛选出三种应用前景良好的绿色催化剂，并实现几种类型的基于酯酰基C-O键的活化的有理论意义和潜在价值的新反应。同时在催化机理方面，对比研究两种催化体系的催化机理，利用非均相催化剂的表征手段得到了较为明确的机理途径。在应用研究方面，我们首次采用内蒙古地区的高岭土矿产合成了高效纳米金属催化剂，并实现了催化醛与苯基吡唑类的邻位导向C-H功能化反应。