Rhodium‐Catalyzed Regioselective N²‐Alkylation of Benzotriazoles with Diazo Compounds/Enynones via a Nonclassical Pathway

A novel rhodium‐catalyzed highly selective N 2 ‐alkylation of benzotriazoles with diazo compounds/enynones is achieved, providing N 2 ‐alkylated benzotriazoles in good to excellent yields and with excellent N 2 selectivities. Importantly, different to traditional carbene insertion into X−H (X=N, O etc) bonds, DFT calculations disclose that this selective N 2 ‐alkylation probably proceeds through a formal 1,3‐ rather than 1,2‐H shift to give the final products.