Phase-transfer catalysis is one of the most useful methodologies for practical syntheses given its operational simplicity and mild reaction conditions that enable its application in industrial processes. Cinchona alkaloids have been a popular, natural source of practical organocatalysts due largely to their excellent commercial availability and low cost. Since the first Cinchona alkaloid-derived phase-transfer catalysts was disclosed in 1981, diverse generations of Cinchona-derived phase-transfer catalysts have been developed and successfully applied to various asymmetric syntheses. In this feature article, we describe the generation of Cinchona-derived chiral phase-transfer catalysts according to the development stages and our efforts toward the design of polymeric Cinchona phase-transfer catalysts, the effects of the electronic functional group incorporated in the catalysts, and their application in asymmetric organic reactions.

The phase-transfer catalytic alkylation of N,N-dialkylmalonamic tert-butyl esters in the presence of 1 mol% of (S,S)-3,4,5-trifluorophenyl-NAS bromide afforded highly enantioselective (S)-mono-α-alkylated products (up to 96% ee), which could be readily converted into versatile chiral building blocks without loss of chirality.