Diastereoselective Synthesis of Bicyclo[3.2.1]octanes via Catalyst‐Free Cascade Michael/Henry Reaction with a Functionalized Vinylogous Nucleophile

Abstract A readily prepared and functionalized vinylogous nucleophile has been explored and utilized to construct bridged bicyclic compounds. The corresponding cascade Michael/Henry reaction occurred with relatively high reactivity under catalyst‐free and mild conditions. A range of structurally distinct bicyclo[3.2.1]octanes were generated in 40–96% isolated yields with excellent diastereoselectivities (≥10:1 dr). Gram‐scale synthesis was also demonstrated.