On-Demand Access to Palladium Oxidative Addition Complexes (OACs) from a Stable Organopalladate Salt

Palladium oxidative addition complexes (OACs) are state-of-the-art catalysts for many C¬–C and C–heteroatom cross-coupling reac-tions, but altering the OAC ancillary ligand identity (i.e., phosphine, N-heterocyclic carbene) often requires a bespoke synthesis. This has limited the modularity and accessibility of these ideal catalysts. We report a simple admixture approach combining a bench-stable or-ganopalladate salt with a mono- or bidentate ligand to generate OACs within minutes at room temperature. High yields across a suite of canonical cross-coupling reactions demonstrates the “on-demand” Pd OAC strategy can function as a drop-in replacement for isolated OACs as well as several other contemporary Pd precatalysts. Characterization of a previously unknown OAC coordinated by a single NHC ligand also highlights how this approach can circumvent decomposition of thermally sensitive OACs that are difficult to access directly from oxidation addition reactions.