Catalytic Asymmetric\nSynthesis of Bicyclic Isothioureas\nfrom a Common Enolizable Template

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