Efficient and Versatile (De)Hydrogenation Catalysts

这是Wilfrid Laurier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脱氢偶联（ADC）反应。我们开发了“绿色”催化方法，用于制造几种主要类型的有机化合物，这些化合物普遍存在于农用化学品、药品、香料和香料以及特种化学品的合成中。本课题的研究目标包括：1)合成一系列氨基硫配体。2)基于上述配体和8族过渡金属（铁、钌、锇）合成一系列双功能催化剂。3)广泛测试了新型催化剂在醇类无受体脱氢偶联（ADC）、酯类、亚胺类和相关底物C=X键加氢反应中的应用。新催化剂将符合学术和工业环境中大型有机制剂的几个实际要求：a)易于在10 - 100g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)负载< 100ppm时的活性，e)低于100℃的活性，最好是在20 - 40℃，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，该小组生产了目前已知的最有效的催化剂，用于将醇转化为羰基化合物（例如乙醇转化为乙酸乙酯），并在氢作用下将酯还原为醇，而不使用危险的氢化铝试剂。拟议的研究预计将提供新的高效和通用的催化剂，允许进行一些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，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.