Merck Center for Catalysis at Princeton University, Princeton, NJ 08544, USA.
Department of Process and Analytical Chemistry, MRL, Merck & Co., Inc., Rahway, NJ 07065, USA.
Science. 2022 Apr 29;376(6592):532-539. doi: 10.1126/science.abn1885. Epub 2022 Apr 28.
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.
反应通用性对于确定合成方法的整体影响和实用性至关重要。典型的通用化方案需要事先的机理理解，并且在应用于复杂且了解较少的体系时会受到限制。我们开发了一种加和映射方法，该方法在生成同时的机理见解的同时，快速扩展了合成方法的实用性。该方法在光诱导金属转移脱羧芳基化反应上的验证，导致发现了一种邻苯二甲酰亚胺配体添加剂，该添加剂克服了该反应的许多遗留限制，并对镍催化交叉偶联反应具有重要的机理意义。
