Synthesis of Benzofulvenes through Rhodium-Catalyzed Transannulation of Enynyl Triazoles.

Rhodium-catalyzed denitrogenative cyclization of (E)-ethyl 2-(1-alkyl and arylsulfonyl-1H-1,2,3-triazol-4-yl)-3-aryl acrylate generated from (E)-ethyl 2-benzylidenebut-3-ynoates and N-sulfonyl azides in the presence of a copper catalyst was developed for the synthesis of a large number of functionalized benzofulvenes. Moreover, the synthesis of benzofulvenes was demonstrated as a one-pot method through tandem copper-catalyzed [3 + 2] cycloaddition and rhodium-catalyzed denitrogenative cyclization from (E)-ethyl 2-benzylidenebut-3-ynoates and N-sulfonyl azides.