Cu-Catalyzed Asymmetric Olefinative Conjugate Addition of Aryl and Alkenyl Boronic Esters

The asymmetric olefinative conjugate addition (AOCA) has been previously introduced as a telescoped approach for the synthesis of chiral internal olefins with high stereoselectivities. Here, this strategy is extended by the implementation of aryl and alkenyl boronic esters as C(sp²) nucleophiles, thus notably expanding the range of accessible products by the AOCA. A variety of relatively complex chiral products are reported, which were obtained in high yields, diastereoselectivities, and enantioselectivities up to 97:3 er. These include dienes and trienes that are otherwise difficult to access in a single step.