Transition metal-catalyzed C-N bond-forming reactions are a staple of modern organic synthesis. In particular, the Buchwald-Hartwig amination reaction is a versatile process for C–N cross-couplings and many research efforts have focused on modifications to this reaction. Our group recently discovered a new class of bimetallic Pd(I) and Pd(II) complexes and showed that these complexes enable cooperative mechanisms where both palladium centers are critical for reactivity. In this report, we describe our efforts to apply these new catalysts to the Buchwald Hartwig and aminocarbonylation reactions. Our Pd(I) dimer enables the rapid formation of the desired C–N cross-coupling. In contrast, our Pd(II) dimer is much more reactive in aminocarbonylation reactions with aryl halides. Our mechanistic studies demonstrate that the starting oxidation state of the bimetallic complex has a large impact on catalytic efficiency and can be an important parameter for optimizing reactions that employ bimetallic catalysts.

2-Phospinoimidazole-derived Pd(I) and Pd(II) dimer catalysts for Buchwald-Hartwig amination and aminocarbonylation reactions

ACS Spring 2022

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