Asymmetric Acyclic 1,3-Difunctionalization of Vinyl Carbenes via Site-Selective Vinylogous Mannich-Type Interception of Oxonium Ylides

A noveland highly stereoselective acyclic 1,3-difunctionalizationof vinyl metal carbene species has been developed via Rh(II)/chiralphosphoric acid co-catalyzed three-component reactions of vinyldiazoacetateswith alcohols and imines. This innovative approach features excellentregio-, diastereo-, and enantioselectivities, demonstrating a broadscope and functional group compatibility. Notably, this is the firstexample of three-component asymmetric acyclic 1,3-difunctionalizationwith in situ-formed vinyl metal carbenes.

Automated summary

A novel and highly stereoselective acyclic 1,3-difunctionalization of vinyl metal carbene species has been developed via Rh(II)/chiral phosphoric acid co-catalyzed three-component reactions of vinyldiazoacetates with alcohols and imines. The reaction demonstrates excellent regio-, diastereo-, and enantioselectivities, and shows a broad scope and functional group compatibility. This study presents the first example of three-component asymmetric acyclic 1,3-difunctionalization with in situ-formed vinyl metal carbenes.