Efficient and Versatile (De)Hydrogenation Catalysts

这是威尔弗里德·劳里埃大学Goussev小组的一个持续研究项目，致力于C=X键的催化氢化和醇的无受体双偶联（ADC）反应。我们开发了“绿色”催化方法，用于生产农用化学品、药物、香精香料和特种化学品合成中普遍存在的几种主要类型的有机化合物。本论文的主要研究内容包括：1）合成一系列具有协同作用的氨基硫醚配体; 2）合成一系列基于上述配体和第8族过渡金属的双功能催化剂（铁、钌和锇）。3）在醇的无受体双偶联（ADC）反应、酯、亚胺和具有C=X键的相关底物的氢化反应中，对新催化剂进行了广泛的测试。新催化剂将符合学术和工业环境中大规模有机制备的几个实际要求：a）易于在10 - 100 g和可能更大的规模上合成催化剂，B）低成本，c）空气稳定性，d）在<100 ppm的负载下的活性，e）低于100 ℃，优选在20 - 40 ℃下的活性，以及d）高官能团耐受性和选择性。拟议的工作建立在NSERC资助的Goussev小组的研究基础上，该研究产生了当今已知的用于将醇转化为羰基化合物的最有效的催化剂（例如乙醇到乙酸乙酯）和用于在氢气下将酯还原成醇，而不使用危险的氢化铝试剂。所提出的研究预计将提供新型高效和通用的催化剂，其将允许进行几种学术和工业上重要的有机合成，遵循绿色化学的原则，即节能，使用低催化剂负载，具有优异的原子效率，并且产生很少或不产生化学废物。

This is a continuing program of research in Goussev's group at Wilfrid Laurier University, devoted to catalytic hydrogenation of C=X bonds and acceptorless dehydrogenative coupling (ADC) reactions of alcohols. We develop 'green' catalytic methods for making several major types of organic compounds ubiquitous in the synthesis of agrochemicals, pharmaceuticals, flavors and fragrances, and specialty chemicals. The objectives of the proposed research include:1) Synthesis of a series of 'cooperating' amino-sulfide ligands.2) Synthesis of a series of bifunctional catalysts based on the above ligands and transition metals from Group 8 (Iron, Ruthenium, and Osmium).3) Extensive testing of the new catalysts in reactions of acceptorless dehydrogenative coupling (ADC)of alcohols, hydrogenation of esters, imines, and related substrates with C=X bonds.The new catalysts will conform to several practical requirements of medium- and large-scale organic preparations in academic and industrial settings: a) ease of catalyst synthesis on 10 - 100 g and possibly larger scale, b) low cost, c) air-stability, d) activity at loadings <100 ppm, e) activity below 100 degrees C, preferably at 20 - 40 degrees C, and d) high functional group tolerance and selectivity.The proposed work builds upon the NSERC-funded research in Goussev's group that produced most efficient catalysts known today for converting alcohols into carbonyl compounds (e.g. ethanol into ethylacetate) and for reduction of esters to alcohols under hydrogen, without using hazardous aluminum hydride reagents. The proposed research is expected to give novel efficient and versatile catalysts that would allow conducting several academically and industrially important organic syntheses following the principles of green chemistry, i.e. energy-saving, using low catalyst loadings, possessing excellent atom-efficiency, and producing little or no chemical waste.