Recent Progress in Asymmetric Ion-Pairing Catalysis with Ammonium Salts.

Quaternary ammonium salts play an important role in asymmetric catalysis. In this Minireview, how asymmetric ion-pairing catalysis with ammonium ions has been utilized in organic synthesis is explained, particularly in the design of novel catalytic cycles. This includes the use of chiral ammonium-based catalysts for the construction of challenging stereogenic centers. Ammonium-derived electrophilic reagents, typically formed in situ and in the context of phase-transfer catalysis (PTC), have also been utilized in asymmetric bond-forming reactions. Furthermore, ammonium salts have been employed as substrates in several stereocontrolled C-N bond cleavage processes, leading to enantioenriched products by using novel asymmetric induction modes. In addition, merging ammonium ion-pairing catalysis with other catalytic approaches has also emerged as a new platform for achieving previously less straightforward reactions, thereby allowing new synthetic applications.