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Towards Substrate–Reagent Interaction of Lochmann–Schlosser Bases in THF: Bridging THF Hides Potential Reaction Site of a Chiral Superbase
Author(s) -
Brieger Lukas,
Schrimpf Tobias,
Scheel Rebecca,
Unkelbach Christian,
Strohmann Carsten
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202202660
Subject(s) - superbase , alkoxide , reagent , chemistry , bimetallic strip , carbanion , metalation , adduct , toluene , substrate (aquarium) , molecule , medicinal chemistry , organic chemistry , catalysis , oceanography , geology
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.