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

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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.