Accelerating reaction generality and mechanistic insight through additive mapping

作者：Cesar N. Prieto Kullmer, Jacob A. Kautzky, Shane W. Krska, Timothy Nowak, Spencer D. Dreher, David W. C. MacMillan · 发表于：Science · 年份：2022 · DOI：10.1126/science.abn1885 · 被引用次数：182 · 研究领域：Catalytic C–H Functionalization Methods、Catalytic Cross-Coupling Reactions、Radical Photochemical Reactions

Reaction generality is crucial in determining the overall impact and usefulness of synthetic methods. Typical generalization protocols require a priori mechanistic understanding and suffer when applied to complex, less understood systems. We developed an additive mapping approach that rapidly expands the utility of synthetic methods while generating concurrent mechanistic insight. Validation of this approach on the metallaphotoredox decarboxylative arylation resulted in the discovery of a phthalimide ligand additive that overcomes many lingering limitations of this reaction and has important mechanistic implications for nickel-catalyzed cross-couplings.