Kinetic Analysis Uncovers Hidden Autocatalysis and Inhibition Pathways in Titanium(III)-Catalyzed Ketone-Nitrile Couplings

Through kinetic analysis, we demonstrate that the formation of catalyst and substrate reservoirs plays a crucial role in titanium(III)-catalyzed ketone-nitrile coupling reaction. Together with insight from previous studies, model is assembled reflects observed influence ZnCl2 Et3N byproducts as well hydrochloride additive, which employed frequently titanium(III) catalysis. We further propose for Cp2TiCl2-catalyzed reaction acceleration phase originates hidden autocatalytic cycle, leads to change rate-determining step over course