Diastereoselective Synthesis of 4-Hydroxy-2-quinolinones via Formal [2 + 4] Cycloaddition Reactions Using α-Diazo Pyrazoleamides as C2 Synthons.

A rhodium-catalyzed highly stereoselective formal [2 + 4]-cycloaddition reaction of α-diazo pyrazoleamides and 2-aminophenyl ketones that produces 4-hydroxy-2-quinolinones in good yields with excellent diastereoselectivities has been developed. A pyrazolium ylide species that is generated from α-diazo pyrazoleamides is used as a C2 synthon for this cycloaddition. This protocol offers an efficient approach to a variety of 4-hydroxy-2-quinolinones featuring sequential quaternary centers.

Silver-catalyzed pyrazole migration and cycloaddition reaction of diazo pyrazoleamides with ketimines.

A novel pyrazole migration and cycloaddition process is well developed via AgOTf-catalyzed annulation reactions of α-diazo pyrazoleamides with ketimines. This protocol discloses efficient access to synthesize a series of spirooxindole-based ß-lactams in good to excellent yields and the diastereoselectivity is switchable by tuning the substituents on the α-diazo pyrazoleamides.

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

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. This innovative approach features excellent regio-, diastereo-, and enantioselectivities, demonstrating a broad scope and functional group compatibility. Notably, this is the first example of three-component asymmetric acyclic 1,3-difunctionalization with in situ-formed vinyl metal carbenes.