In Situ Catalyst Generation and Benchtop-Compatible Entry Points for Ti<sup>II</sup>/Ti<sup>IV</sup> Redox Catalytic Reactions

The development of several in situ generated catalyst systems for Ti-catalyzed oxidative nitrene transfer reactions is reported. The simplest and widely applicable catalyst system, TiCl<sub>4</sub>(THF)<sub>2</sub>/Zn<sup>0</sup>, can be set up on the benchtop under air. This system uses commercially available reagents and can be used as an entry point for Ti<sup>II</sup>/Ti<sup>IV</sup> multicomponent redox reactions for the synthesis of pyrroles, α,γ-unsaturated imines, α,β-unsaturated imines, cyclopropylimines, and arenes.