Desulfitative Redox Catalysis: A New Paradigm for Carbon-Carbon and Carbon-Nitrogen Bond Formation

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In this project funded by the Chemical Catalysis program of the Chemistry Division of the National Science Foundation, Professor Lanny S. Liebeskind and his coworkers of Emory University are developing a new, atom-efficient, environmentally-sensitive catalytic system for the production of amides (and peptides), esters, and ketones directly from carboxylic acids. This new reaction system possesses a number of the key attributes that are desired for environmentally sustainable 21st century "green" chemical synthesis: the minimization of chemical waste, the avoidance of hazardous reagents, the use of benign solvents and reagents, the use of environmentally sustainable feedstocks, and the use of ambient temperatures to maximize energy efficiencies.This new reaction system currently under development relies, in part, on the use of non-toxic redox organocatalysts that are easily recycled using oxygen in air. In combination with an inexpensive phosphite, the redox organocatalyst drives the dehydrative formation of carbon-carbon, carbon-nitrogen, and carbon-oxygen bonds from carboxylic acids. The broader societal impact of this work derives from its introduction of a new "redox organocatalytic" paradigm for chemical synthesis that establishes an environmentally sustainable means by which hydroxylic reactants, like carboxylic acids, can be transformed into value added materials like amides/peptides, esters, and ketones using "green" chemistry principles. It can positively impact chemical synthesis across various domains (commodities, fine chemicals, biologicals) and its development represents an excellent tool for training students and postdoctoral associates in the rigors of critical scientific thinking and analysis.