Stereodivergent Synthesis of Three Contiguous Stereogenic Centers by Cu/Ir‐Catalyzed Borylallylation

Abstract Polyfunctional compounds bearing multiple stereogenic centers are synthetically valuable and important for complex molecule preparation. Herein, a Cu/Ir‐catalyzed borylallylation of electron deficient alkenes is presented. The reaction operates by the cooperative function of a chiral Cu‐complex and a chiral Ir‐complex to generate products with high levels of stereocontrol. The method also allows for the stereodivergent synthesis of acyclic products with control of three stereogenic centers. Importantly, the products contain C─B, ester, and alkene functionalities, which allows for a diverse range of products to be generated. Finally, the highly functional nature of the products has been exploited in an efficient formal synthesis of the complex natural product (+)‐(β)‐Lycorane.