Substrate-Dependent Denitrogenative Rearrangements of Rhodium Azavinyl Carbenes Involving 1,2-Aryl Migration.

Herein, we disclose substrate-dependent rearrangements of 4-substituted N -sulfonyl-1,2,3-triazoles under Rh(II)-catalysis via denitrogenation. The reaction pathways included key 1,2-aryl migration via the formation of intermediatory phenonium ion, which is elusive so far with Rh-azavinyl carbenes. Intriguingly, the transformations were completely dependent on the substituent present leading to different scaffolds like enaminones, pyrrol-3-ones, and azadienes. Hammett studies provided essential insights into the carbocationic intermediate formation. The developed methodology featured simple reaction conditions, excellent functional group compatibility, and broad substrate scope.