Stereodivergent Construction of Csp3−Csp3 Bonds Bearing Vicinal Stereocenters by Synergistic Palladium and Phase‐Transfer Catalysis

摘要

Abstract Synergistic catalysis has emerged as one of the most powerful tools for stereodivergent formation of Csp3−Csp3 bonds bearing vicinal stereocenters. Despite the many successes that have been achieved in this field, stereodivergent Csp3−Csp3 coupling reactions involving stabilized nucleophiles remain challenging because of the competing single‐catalysis pathway. Herein, we report a synergistic palladium/phase‐transfer catalyst system that enables diastereodivergent Csp3−Csp3 coupling reactions of 1,3‐dienes with stabilized nucleophile oxindoles. Both the syn and anti coupling products, bearing quaternary and tertiary vicinal stereocenters, could be selectively produced in good yields with high enantio‐ and diastereoselectivities. Non‐covalent activation of the stabilized nucleophile via chiral ion pair in a biphasic system is a crucial success factor in achieving diastereodivergence.