Recent advances towards organocatalytic enantioselective desymmetrizing reactions

Enantioselective desymmetrization is an attractive and effective method for the straightforward assembly of versatile chiral molecules. The rapid development of organocatalysis has offered a rich platform for desymmetrizing reactions by providing novel organocatalysts and activation modes. A range of available feedstocks, including ketones, diketones, diols, enones, dienes, small rings, and other prochiral substrates, can be used in organocatalytic desymmetrizing processes in a stereocontrollable fashion. The practical application of organocatalytic desymmetrization in the construction of diverse bioactive molecules and natural products is highly expected in the near future. Desymmetrization of prochiral or meso-substrates bearing pre-existing stereogenic centers has proven to be a practical and efficient strategy in synthetic chemistry and has attracted tremendous attention for its utility in the facile assembly of valuable molecular complexity, especially in an enantioselective and diastereoselective manner. Simultaneously, organocatalysis has arguably become a powerful toolbox in asymmetric catalysis since its inception, thus capable of providing new opportunities for desymmetrizing transformations. The past 5 years have witnessed remarkable progress in the combination of organocatalysis with desymmetrization, and considerable relevant cases have been successively demonstrated. Organized on the basis of substrate class, this review comprehensively presents a summary of recent advances achieved in this fruitful field, aimed at highlighting the reactions’ features, practicalities, and mechanisms. Desymmetrization of prochiral or meso-substrates bearing pre-existing stereogenic centers has proven to be a practical and efficient strategy in synthetic chemistry and has attracted tremendous attention for its utility in the facile assembly of valuable molecular complexity, especially in an enantioselective and diastereoselective manner. Simultaneously, organocatalysis has arguably become a powerful toolbox in asymmetric catalysis since its inception, thus capable of providing new opportunities for desymmetrizing transformations. The past 5 years have witnessed remarkable progress in the combination of organocatalysis with desymmetrization, and considerable relevant cases have been successively demonstrated. Organized on the basis of substrate class, this review comprehensively presents a summary of recent advances achieved in this fruitful field, aimed at highlighting the reactions’ features, practicalities, and mechanisms. molecules or ions that can donate protons. a process that realizes desymmetrization of sp2-hybrized prochiral carbons. a description of the relationship between a pair of functional groups that can furnish enantiomers when one is transformed. a process to separate one configuration of racemic substrates into the corresponding enantiomers. molecules or ions that can donate paired electrons. compounds that bear stereocenters but exhibit as optically inactive due to other intrinsic symmetry elements. a structural unit that can be utilized to synthesize one product through some specific reactions.