Efficient Access to Titanaaziridines by CH Activation of N‐Methylanilines at Ambient Temperature

Titanaaziridines or η²‐imine titanium complexes are considered key intermediates of the titanium‐catalyzed hydroaminoalkylation of alkenes. Herein, we present an efficient synthetic route to this class of compounds, starting from N‐methylanilines and a bis(η⁵:η¹‐pentafulvene)titanium complex. Consecutive reactions on the η²‐methyleneaniline complexes, characterized for the first time, prove a high chemical versatility. In particular, hydroaminoalkylation products were found in reactions of the three‐membered titanacycles with alkenes. For the first time, all the intermediates of the hydroaminoalkylation of alkenes were isolated and characterized.