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脱氢偶联(ADC)反应。我们开发了绿色催化方法来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。这项研究的目标包括：1)合成一系列‘协作型’氨基硫化物配体。2)合成一系列基于上述配体和8族过渡金属(铁、钚和锶)的双功能催化剂。3)对新型催化剂在醇的无受体脱氢偶联(ADC)反应、酯、亚胺和C=X键的相关底物的加氢反应中进行广泛的测试。新催化剂将符合学术和工业环境中对中型和大型有机制剂的几个实际要求：a)10-100克或可能更大规模的催化剂合成容易，b)低成本，b)催化剂合成成本低C)空气稳定性；d)装载时的活动性；100ppm，e)低于100摄氏度，最好是20-40摄氏度，以及d)高的官能团耐受性和选择性。拟议的工作建立在NSERC资助的Goussev团队的研究基础上，该研究生产了当今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)，以及在氢气下将酯还原为醇，而不使用危险的氢化铝试剂。这项拟议的研究有望提供新型、高效和通用的催化剂，使一些在学术和工业上具有重要意义的有机合成能够遵循绿色化学的原则进行，即节能、使用低催化剂、具有优异的原子效率、产生很少或根本没有化学废物。

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.