Advanced sustainable and clean "all-in-one" catalytic technologies for the dehydrogenative coupling of alcohols and reduction of carbonyl functionalities

催化是现代清洁化学技术的基础，被统称为“绿色化学”。我们的研究旨在发现和开发实用的工业相关催化剂，用于极性键的加氢和脱氢-这一过程允许获得广泛的醇和羧酸衍生物。羧酸、羧酸酯和羧胺是天然产物和合成有机化合物（如药品、农用化学品、香精和香料）中普遍存在的功能。我们最近的工作清楚地表明，羰基的催化加氢与伯醇的脱氢偶联反应产生酯和酰胺具有内在的机制联系。因此，我们有兴趣设计高效的“一体化”催化剂，能够将羰基官能团转化为相应的醇，并在需要时完成羧酸衍生物的逆向合成。我们提出，理想的合成/还原羧酸酯的“一体化”催化剂应该是在配体主链中具有指向N-H基团的多齿配体的稳定配位环境中具有热鲁棒性的金属氢化物。我们小组最近的一些研究进一步提倡开发基于相对“软”的刘易斯酸金属离子的新催化剂，例如一些5d金属和低氧化态的晚期过渡金属。在这方面，对丰富的非贵重d金属的催化潜力的研究特别有趣。高效镍、铜、锌或钨催化剂的发现将对工业和学术界产生重大影响。提出的研究具有很强的学术成分，将推进我们对催化的基本理解，提高极性键氧化还原转化的效率和可持续性。我们期望发现更广泛的趋势和从d区金属的性质和它们的催化行为之间的联系。这些知识对于合理的催化剂设计是必不可少的。由于这项研究是由研究小组与一组本科生和研究生合作进行的，因此该项目对培养未来的科学家具有很大的潜力。

Catalysis is the foundation of modern clean chemical technologies collectively known as "green chemistry". Our research is aimed at discovering and developing practical industry-relevant catalysts for the hydrogenation and dehydrogenation of polar bonds - processes allowing access to a broad range of derivatives of alcohols and carboxylic acids. Carboxylic acids, their esters and carboxamides are ubiquitous functionalities of natural products and synthetic organic compounds such as pharmaceuticals, agrochemicals, flavors, and fragrances. Our recent work clearly indicates that catalytic hydrogenation of the carbonyls is intrinsically mechanistically connected with the dehydrogenative coupling reactions of primary alcohols leading to esters and amides. Thus, we are interested in designing efficient "all-in-one" catalysts capable of converting the carbonyl functionalities into the corresponding alcohols and, when desirable, accomplishing the reverse syntheses of the carboxylic acid derivatives. We propose that an ideal "all-in-one" catalyst for the synthesis/reduction of carboxylates should be a thermally-robust metal hydride in a stable coordination environment of a polydentate ligand possessing a directing N-H group in the ligand backbone. Some of the most recent research from our group further advocates the development of new catalysts based on the relatively "soft" Lewis acid metal ions, such as some of the 5d metals and the late transition metals in low oxidation states. In this regard, the investigation of the catalytic potential of the abundant, non-precious d-metals is particularly intriguing. Discovery of efficient nickel, copper, zinc, or tungsten catalysts will have a major impact in both industry and academia. The proposed research has a strong academic component that will advance our fundamental understanding of catalysis and increase the efficiency and sustainability of redox transformations of polar bonds. We expect to discover broader trends and connections between the properties of the metals from the d-block and their catalytic behavior. This knowledge is essential for rational catalyst design. As the research is conducted by the PI in collaboration with a group of undergraduate and graduate students, the project has a strong potential to facilitate the training of future scientists.