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

在这个由美国国家科学基金会化学部化学催化项目资助的项目中，埃默里大学的Lanny S. Liebeskind教授和他的同事正在开发一种新的、原子高效的、对环境敏感的催化系统，用于直接从羧酸中生产酰胺（和肽）、酯和酮。这种新的反应系统具有21世纪环境可持续的“绿色”化学合成所需的一些关键属性：最大限度地减少化学废物，避免危险试剂，使用良性溶剂和试剂，使用环境可持续的原料，以及使用环境温度来最大限度地提高能源效率。目前正在开发的这种新的反应系统部分依赖于使用无毒氧化还原有机催化剂，这种催化剂很容易在空气中使用氧气进行回收。与廉价的亚磷酸酯结合，氧化还原有机催化剂驱动羧酸的碳-碳、碳-氮和碳-氧键的脱水形成。这项工作的更广泛的社会影响源于它引入了一种新的化学合成“氧化还原有机催化”范式，该范式建立了一种环境可持续的方法，通过这种方法，羟基反应物，如羧酸，可以利用“绿色”化学原理转化为酰胺/肽、酯和酮等增值材料。它可以对各个领域（商品、精细化学品、生物制品）的化学合成产生积极影响，它的发展是培养学生和博士后严谨的批判性科学思维和分析能力的绝佳工具。

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.