Towards Substrate–Reagent Interaction of Lochmann–Schlosser Bases in THF: Bridging THF Hides Potential Reaction Site of a Chiral Superbase

The metalation of N,N‐dimethylaminomethylferrocene in THF by the superbasic mixture of ( n )BuLi/KO( t )Bu proceeds readily at low temperatures to afford a bimetallic Li(2)K(2) aggregate containing ferrocenyl anions and tert‐butoxide. Starting from an enantiomerically enriched ortho‐lithiated aminomethylferrocene, an enantiomerically pure superbase can be prepared. The molecular compound exhibits superbasic behavior deprotonating N,N‐dimethylbenzylamine in the α‐position and is also capable of deprotonating toluene. Quantum chemical calculations provide insight into the role of the bridging THF molecule to the possible substrate–reagent interaction. In addition, a benzylpotassium alkoxide adduct gives a closer look into the corresponding reaction site of the Lochmann–Schlosser base that is reported herein.