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，统称为“绿色化学”。我们的研究旨在发现和开发与工业相关的实用催化剂，用于极性键的加氢和脱氢-允许获得广泛的醇和羧酸衍生物的过程。羧酸及其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、香料和香料)的普遍功能。我们最近的工作清楚地表明，羰基的催化氢化与伯醇的脱氢偶联反应在本质上是机械联系的，从而产生酯和酰胺。因此，我们对设计高效的“一体式”催化剂感兴趣，该催化剂能够将羰基官能团转化为相应的醇，并在需要的情况下完成羧酸衍生物的反向合成。我们认为，理想的合成/还原羧酸盐的“一体式”催化剂应该是一种耐热的金属氢化物，其配位环境稳定，配体主链上具有定向N-H基团的多齿配体。我们小组的一些最新研究进一步倡导开发基于相对“软”的Lewis酸性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，对丰富的、非贵金属的催化潜力的研究特别耐人寻味。高效镍、铜、锌或钨催化剂的发现将对工业界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，并提高极性键的氧化还原转换的效率和可持续性。我们希望发现d-块金属的性质和它们的催化行为之间更广泛的趋势和联系。这些知识对于合理的催化剂设计是必不可少的。由于这项研究是由国际和平研究所与一群本科生和研究生合作进行的，该项目有很大的潜力促进未来科学家的培训。

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.