Abstract
Ti-catalyzed oxidative alkyne carboamination with alkenes and azo compounds can yield either α,β-unsaturated imines or cyclopropyl imines through a common azatitanacyclohexene intermediate. Herein, we report the synthesis of a model azatitanacyclohexene complex (3) through the ring-opening of a cyclopropyl imine with Cp(2)Ti(BTMSA) (BTMSA = bis(trimethylsilyl)acetylene). 3 readily undergoes thermal or reductant-catalyzed ring contraction to an azatitanacyclopentene (4), analogous to the proposed mechanism for forming α,β-unsaturated imines in the catalytic reaction. A cyclopropyl imine or an α,β-unsaturated imine could be liberated via the oxidation of 3 or 4 with azobenzene, respectively, further implicating the role of these metallacycles in the Ti-catalyzed carboamination reaction.