Recent Advances in the Asymmetric Doyle–Kirmse Reaction

Abstract The asymmetric Doyle–Kirmse reaction has become increasingly important in the construction of chiral sulfides, especially for those with quaternary carbon stereocenters. Over the few past decades, a series of catalytic asymmetric approaches have been developed promoted by copper, rhodium, nickel, and other chiral catalysts. Apart from the frequently investigated sulfonium ylides, the enantioselective [2,3]-sigmatropic rearrangement of selenium ylides and iodonium ylides has also been discovered recently. This review summarizes recent advances in the asymmetric Doyle–Kirmse reaction according to the patterns of chirality induction. The synthetic methods for rearranged products, reaction mechanisms and applications are discussed in this review. 1 Introduction 2 Asymmetric Doyle–Kirmse Reaction Controlled by Chiral Free Ylides 3 Asymmetric Doyle–Kirmse Reaction Controlled by Chiral Metal-Bound Ylides 4 Conclusion and Outlook