Enantioselective Desymmetrization of 1,3‐Dicarbonyl Compounds through Transition‐Metal‐Catalyzed Intramolecular Cyclization Reactions

The development of reliable approaches to construct enantioenriched cyclic ketones bearing multiple stereocenters has attracted intense interest in synthetic chemistry, yet remains a challenging research area due to the difficulties in efficiently controlling the reaction enantioselectivity and diastereoselectivity. Desymmetrization of C2‐symmetric prochiral substrates has witnessed a practical and accessible strategy for creating more than one stereocenters in a single operation. In recent years, enantioselective desymmetrization of 1,3‐dicarbonyl compounds has been developed via transition‐metal‐catalyzed transformations for facile assembly of optically active cyclic ketones bearing congested stereocenters with diverse functionality. In this review, we would like to describe intramolecular enantioselective desymmetrization reactions of 1,3‐dicarbonyl derivatives, including C2‐functional group tethered 1,3‐diketones and 1,3‐diesters. This review is organized according to types of tethered groups, which aims to highlight the recent advances and briefly discuss about future perspectives in this domain.