Regiodivergent Metal-Catalyzed Rearrangement of 3-Iminocyclopropenes into N-Fused Heterocycles

A highly efficient regiodivergent method for the synthesis of N-fused heterocycles via transition-metal-catalyzed rearrangement of 3-iminocyclopropenes has been developed

Direct Palladium-Catalyzed Arylation of Cyclopropenes

The first examples of direct palladium-catalyzed arylation and heteroarylation of cyclopropenes have been demonstrated. This method allows for efficient synthesis of various tetrasubstituted cyclopropenes, incuding nonracemic cyclopropenes, which are not available via known asymmetric cyclopropenation methods. Mechanistic studies strongly suggest an electrophilic path for this Heck-type transformation

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

Direct Pd-Catalyzed Arylation of 1,2,3-Triazoles^†

A highly efficient method for the synthesis of multisubstituted 1,2,3-triazoles via a direct Pd-catalyzed C-5 arylation has been developed

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

Catalytic Asymmetric C–H Insertions of Rhodium(II) Azavinyl Carbenes

A highly efficient enantioselective C–H insertion of azavinyl carbenes into unactivated alkanes has been developed. These transition metal carbenes are directly generated from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of chiral Rh(II) carboxylates and are used for C–H functionalization of alkanes to access a variety of β-chiral sulfonamides

Catalytic Asymmetric C–H Insertions of Rhodium(II) Azavinyl Carbenes

A highly efficient enantioselective C–H insertion of azavinyl carbenes into unactivated alkanes has been developed. These transition metal carbenes are directly generated from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of chiral Rh(II) carboxylates and are used for C–H functionalization of alkanes to access a variety of β-chiral sulfonamides

Sila Morita−Baylis−Hillman Reaction of Cyclopropenes

The first example of sila-Morita-Bayis-Hillman reaction between 1-silylcyclopropenes and carbonyl compounds has been demonstrated. This novel phosphine-catalyzed transformation features a 1,3-Brook rearrangement/elimination cascade and provides convenient access to a variety of 1-(silyloxymethyl)cyclopropenes, which are not easily available via traditional methods

Fused Tetrazoles as Azide Surrogates in Click Reaction: Efficient Synthesis of N-Heterocycle-Substituted 1,2,3-Triazoles

It has been shown that various pyrido-, quinolino-, pyrazino-, and quinoxalinotetrazoles can be used efficiently as azide components in Cu-catalyzed click reaction with alkynes. This method allows for efficient synthesis of a wide variety of N-heterocyclic derivatives of 1,2,3-triazoles