Highly diastereo- And enantioselective synthesis of quinuclidine derivatives by an iridium-catalyzed intramolecular allylic dearomatization reaction

Abstract

Asymmetric construction of quinuclidine derivatives has been realized by an iridium-catalyzed allylic dearomatization reaction. The catalytic system, derived from [Ir(cod)Cl]2 and the Feringa ligand, tolerates a broad range of substrates. A large array of quinuclidine derivatives can be obtained under mild conditions in good to excellent yields (68%-96%), diastereoselectivity (up to >20/1 dr), and enantioselectivity (up to >99% ee). These products feature versatile functional group diversity and can undergo diverse transformations. A model that accounts for the origin of the stereoselectivity has been proposed based on density functional theory (DFT) calculations.