Cationic Organic Catalysts or Ligands in Concert with Metal Catalysts

Cooperative dual catalysis and bifunctional catalysis have emerged as reliable strategies for the development of hitherto difficult asymmetric transformations because they could deliver new reactivity and selectivity, and allow for the employment of substrates not amenable to reaction systems relying on a single, monofunctional catalysts. Furthermore, these modes of catalysis often improve yields and stereoselectivities via the precise recognition and simultaneous activation of nucleophiles and electrophiles. Efforts towards utilizing chiral cationic organic catalysts for asymmetric cooperative catalysis with metal complexes have provided a unique platform to address the challenging issues associated with reaction development. Chiral onium ions, such as tetraalkylammonium, guanidinium, and azolium ions, are employed mainly to control the reactivity and stereochemistry of anionic intermediates through electrostatic and hydrogen-bonding interactions. Metal complexes complement the synergy of the catalysis by activating the substrates via the formation of electrophilic π-allyl complexes, Lewis acid–base adducts, nucleophilic ate complexes, etc. The electrostatic interactions between cations and anions also offer a means to construct complex molecular assemblies, and, thus, onium ions are useful not only for controlling pairing with anionic species, but also for the design of supramolecular catalysts. The combination of onium ions and metal complexes leads to the introduction of novel concepts and powerful strategies for the development of catalysts and chemical transformations.