Catalyst design is a key research area in modern synthetic chemistry. Engineering of molecular catalysts in homogeneous catalysis brings about new catalytic modes that enable efficient synthetic transformations. In this regard, design of novel ligands for transition-metal catalysis have played a major role. Olefins have been emerging as a significant class of steering ligands in transition-metal catalysis, which are known to serve as innocent ligands that provide electronic and steric tuning of the metal center. However, it is unknown whether a distinct type of olefin ligand that contrasts the common innocent feature is possible. Here we show that a novel type of heteroatom-cycloolefin hybrid ligand functions as a non-innocent ligand in palladium catalysis, which exhibits covalent catalytic function that enables efficient ipso,ortho-difunctionalization of iodoarenes. Detailed mechanistic study revealed that this ligand undergoes reversible covalent bonding between the substrate and the cycloolefin unit, which forms key organopalladium intermediates to enable new reactivity. Our results demonstrate a novel design concept that utilizes unstrained cycloolefin as a covalent catalytic module, opening an avenue to a more general transition metal/olefin cooperative catalysis.
Non-innocent hybrid cycloolefin ligands for palladium/olefin cooperative catalysis