An inventive approach to the development of chiral Bronsted acid catalysis, to enable catalysts which possess strong acid functionalities, has been accomplished. Among the various organic Brønsted acids surveyed, phosphoricacids have become the focus of our attention as potential chiral Brønsted acid catalysts because of theirunique structural and chemical features. The desirable features of phosphoricacids as chiral Brønsted acid catalysts are summarized as follows. 1) Phosphoricacids are expected to have relatively strong yet appropriate acidity. 2) The phosphoryl oxygen would function as a Brønsted basicsite and hence it is anticipated that it would convey acid/base dual function even to monofunctional phosphoric acid catalysts. 3) An acidic functionality is available even with the introduction of a ring system which effectively restricts the conformational flexibility of the chiral backbone. 4) Substituents can be introduced to the ring system to provide an efficient chiral environment for enantioselective transformations. It is anticipated that an efficient substrate recognition site would be constructed around the activation site due to the acid/base dualfunction and the steric and electronic influence of the substituents introduced at the ring system. In this context, we developed 1,1′-bi- 2-naphthol (BINOL)-derived monophosphoricacids as chiral Brønsted acid catalysts. The chiral phosphoricacids thus developed functioned as efficient enantioselective catalysts for a variety of carbon-carbon bond forming reactions via activation of a series offunctionalities, affording enantioenriched products in excellent selectivities. In this article, we review our recent achievements in developing enantioselective reactions using the chiral phosphoricacid catalysts. The contents are arranged according to the type offunctionality, including imines, hemiaminal ethers, aldehydes, and electronrich double bonds, followed by specific reaction types.
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