Ligand Activity Trends in the Buchwald–Hartwig Amination Reaction: Theory and Experiments

Herein, we correlate the predicted ligand activity trends from density functional theory (DFT)-derived volcano plots with reaction rates estimated from experiments. We use the palladium-catalyzed Buchwald–Hartwig amination (BHA) reaction between bromobenzene and n-butylamine as the model reaction with the aim to establish volcano plots as a visual guide to rationalize reactivity and, hence, design new catalysts for the BHA reaction. Overall, the experimental results show alignment with theoretical predictions, and the interpretation of observed deviations is discussed.