Accelerating reaction generality and mechanistic insight through additive mapping

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.

Automated summary

The generality of a reaction is crucial for determining its overall impact and usefulness in synthetic methods. This study developed an additive mapping approach that rapidly expands the utility of synthetic methods and provides mechanistic insight. By validating this approach on a specific reaction, the discovery of a phthalimide ligand additive was made, which overcomes limitations and has important mechanistic implications for nickel-catalyzed cross-couplings.