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

Titanaaziridines or eta(2)-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(eta(5):eta(1)-pentafulvene) titanium complex. Consecutive reactions on the eta(2)-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.