Dual-Catalysis-Enabled Construction of Vicinal Stereogenic Centers through Diastereo- and Enantioselective Allylic Substitution

Vicinal stereogenic centers represent prevalent structuralmotifs in organic synthetic chemistry, and their construction poses alongstanding challenge. Transition-metal-catalyzed asymmetric allylicsubstitution has become a well-established enantioselective C-C bond-forming reaction. When these reactions involve a prochiral nucleophileand an allylic electrophile with a terminal substituent, the creation ofvicinal stereogenic centers becomes feasible. However, despite remark-able achievements having been accomplished, realizing this transfor-mation with precise control over both the enantio- and diastereoselec-tivity remains a significant challenge. To address the stereoselectivechallenges, the introduction of a second catalyst to the transition-met-al-catalyzed asymmetric allylic alkylation to control the diastereoselec-tivity during C-C bond formation has proven particularly fruitful. In thisshort review, we aim to highlight recent advances in dual catalysis thatenable diastereo- and enantioselective allylic substitutions.