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 reactions,
but altering the 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 organopalladate
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 demonstrate 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 the decomposition of thermally sensitive
OACs that are difficult to access directly from oxidation addition
reactions.