Catalytic Asymmetric Synthesis of Bicyclic Isothioureas from a Common Enolizable Template

While bicyclic isothiourea (ITU) moieties are found in biologically active molecules and organocatalysts, a catalytic asymmetric synthesis of ITUs is pending. Here, we report the catalytic, enantioselective functionalization of enolizable template <b>II</b> with a variety of electrophiles, including unsaturated ketones, esters, sulfones, nitro compounds, and thiolating reagents, as an entry to enantioenriched bicyclic ITUs <b>III</b>. Scope and limitations are shown, as well as examples of product derivatization.