Copper-catalyzed asymmetric allylic substitution of racemic/ substrates.

The synthesis of enantiomerically pure compounds is a pivotal subject in the field of chemistry, with enantioselective catalysis currently standing as the primary approach for delivering specific enantiomers. Among these strategies, Cu-catalyzed asymmetric allylic substitution (AAS) is significant and irreplaceable, especially when it comes to the use of non-stabilized nucleophiles (p > 25). Although Cu-catalyzed AAS of prochiral substrates has also been widely developed, methodologies involving racemic/ substrates are highly desirable, as the substrates undergo dynamic processes to give single enantiomer products. Inspired by the pioneering work of the Alexakis, Feringa and Gennari groups, Cu-catalyzed AAS has been continuously employed in deracemization and desymmetrization processes for the synthesis of enantiomerically enriched products. In this review, we mainly focus on the developments of Cu-catalyzed AAS with racemic/ substrates over the past two decades, providing an explicit outline of the ligands employed, the scope of nucleophiles, the underlying dynamic processes and their practical applications.