Leveraging Metal and Ligand Reactive Sites for One Pot Reactions: Ligand‐Centered Borenium Ions for Tandem Catalysis with Palladium

Tandem catalysts that perform two different organic transformations in a single pot are highly desirable because they enable rapid and efficient assembly of simple organic building blocks into more complex molecules. Many examples of tandem catalysis rely on metal-catalyzed reactions involving one or more metal complexes. Remarkably, despite surging interest in the development of chemically reactive (i. e., non-innocent) ligands, there are few examples of metal complexes that leverage ligand-centered reactivity to perform catalytic reactions in tandem with separate catalytic reactions at the metal. Here we report how multifunctional Pd complexes with triaminoborane-derived diphosphorus ligands, called TBDPhos, appear to facilitate borenium-catalyzed cycloaddition reactions at the ligand, and Pd-catalyzed Stille and Suzuki cross-coupling reactions at the metal. Both transformations can be accessed in one pot to afford rare examples of tandem catalysis using separate metal and ligand catalysis sites in a single complex.