Transition metal-catalyzed synthesis of cyclopropenes and N-fused heterocycles.

Transition metal-catalyzed synthesis of cyclopropenes and N-fused heterocycles

Transannulation of 1‑Sulfonyl-1,2,3-triazoles with Heterocumulenes

Readily available 1-mesyl-1,2,3-triazoles are efficiently converted into a variety of imidazolones and thiazoles by Rh­(II)-catalyzed denitrogenative reactions with isocyanates and isothiocyanates, respectively. The proposed triazole–diazoimine equilibrium results in the formation of highly reactive azavinyl metal-carbenes, which react with heterocumulenes causing an apparent swap of 1,2,3-triazole core for another heterocycle

Transannulation of 1‑Sulfonyl-1,2,3-triazoles with Heterocumulenes

Readily available 1-mesyl-1,2,3-triazoles are efficiently converted into a variety of imidazolones and thiazoles by Rh­(II)-catalyzed denitrogenative reactions with isocyanates and isothiocyanates, respectively. The proposed triazole–diazoimine equilibrium results in the formation of highly reactive azavinyl metal-carbenes, which react with heterocumulenes causing an apparent swap of 1,2,3-triazole core for another heterocycle

Transannulation of 1‑Sulfonyl-1,2,3-triazoles with Heterocumulenes

Readily available 1-mesyl-1,2,3-triazoles are efficiently converted into a variety of imidazolones and thiazoles by Rh­(II)-catalyzed denitrogenative reactions with isocyanates and isothiocyanates, respectively. The proposed triazole–diazoimine equilibrium results in the formation of highly reactive azavinyl metal-carbenes, which react with heterocumulenes causing an apparent swap of 1,2,3-triazole core for another heterocycle

Arylation of Rhodium(II) Azavinyl Carbenes with Boronic Acids

A highly efficient and stereoselective arylation of in situ-generated azavinyl carbenes affording 2,2-diaryl enamines at ambient temperatures has been developed. These transition-metal carbenes are directly produced from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of a rhodium carboxylate catalyst. In several cases, the enamines generated in this reaction can be cyclized into substituted indoles employing copper catalysis

Arylation of Rhodium(II) Azavinyl Carbenes with Boronic Acids

A highly efficient and stereoselective arylation of in situ-generated azavinyl carbenes affording 2,2-diaryl enamines at ambient temperatures has been developed. These transition-metal carbenes are directly produced from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of a rhodium carboxylate catalyst. In several cases, the enamines generated in this reaction can be cyclized into substituted indoles employing copper catalysis

Stereoselective 1,3-Insertions of Rhodium(II) Azavinyl Carbenes

Rhodium­(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild, and convergent formal 1,3-insertion into N–H and O–H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bisfunctionalized (<i>Z</i>)-olefins with perfect regio- and stereoselectivity. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition-metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles

Stereoselective 1,3-Insertions of Rhodium(II) Azavinyl Carbenes

Rhodium­(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild, and convergent formal 1,3-insertion into N–H and O–H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bisfunctionalized (<i>Z</i>)-olefins with perfect regio- and stereoselectivity. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition-metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles

Stereoselective 1,3-Insertions of Rhodium(II) Azavinyl Carbenes

Rhodium­(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild, and convergent formal 1,3-insertion into N–H and O–H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bisfunctionalized (<i>Z</i>)-olefins with perfect regio- and stereoselectivity. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition-metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles