Intramolecular Hydride Transfer Racemization Coupled with Enzymatic Kinetic Resolution Enables Asymmetric Syntheses of Caged Compounds

Abstract Caged molecules featuring the pentacycloundecane framework and related substructures represent an exciting class with numerous potential applications, yet reports of their asymmetric syntheses are scarce. In this work, we report a method for the asymmetric synthesis of these compounds, featuring the combined effect of a lipase-catalyzed kinetic resolution and the unique ability of the hydroxyketone starting materials to racemize via an intramolecular hydride transfer. This particular racemization, although previously reported, had, until this study, not been utilized in a synthetic context.