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，用于极性键的氢化和脱氢-工艺允许获得广泛的醇和羧酸衍生物。羧酸、其酯和羧酰胺是天然产物和合成有机化合物如药物、农用化学品、调味剂和香料的普遍存在的官能团。我们最近的工作清楚地表明，羰基化合物的催化氢化与伯醇的缩合偶联反应产生酯和酰胺的内在机理有关。因此，我们感兴趣的是设计有效的“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，实现羧酸衍生物的逆合成。我们建议，一个理想的“所有在一个”催化剂的合成/还原羧酸盐应该是一个热鲁棒的金属氢化物在一个稳定的多齿配体的配位环境中具有指导N-H基团的配体骨架。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金属和低氧化态的后过渡金属。在这方面，调查的催化潜力丰富，非贵d-金属是特别有趣的。高效镍、铜、锌或钨催化剂的发现将在工业和学术界产生重大影响。拟议的研究具有很强的学术成分，将促进我们对催化的基本理解，并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d区金属性质与其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PI与一组本科生和研究生合作进行的，因此该项目具有促进未来科学家培训的强大潜力。

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.