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 II with a variety of electrophiles, including unsaturated ketones, esters, sulfones, nitro compounds, and thiolating reagents, as an entry to enantioenriched bicyclic ITUs III. Scope and limitations are shown, as well as examples of product derivatization.