Tuning Reactivities of tert-Butyllithium by the Addition of Stoichiometric Amounts of Tetrahydrofuran.
Chemistry
; 30(16): e202304226, 2024 Mar 15.
Article
em En
| MEDLINE
| ID: mdl-38189898
ABSTRACT
In alkyllithium chemistry the highest reactivity has historically been linked to the smallest degree of aggregation possible. Since tert-butyllithium is known to form a monomer in tetrahydrofuran solution, using just stoichiometric amounts of the lewis base to selectively form a dimeric species seemed irrational. In this study, we showed a considerable increase of the reactivity of t-BuLi when using stoichiometric amounts of THF in the non-polar solvent n-pentane in order to enable the deprotonation of simple methyl silanes and other low C-H-acidic substrates. In this context, we were able to obtain the corresponding aggregates of t-BuLi with the ligand THF in suspension and as crystalline solids and investigate them by single crystal X-ray structural analysis, inâ
situ FTIR spectroscopy and quantum chemical calculations. Furthermore, we were able to explain the enhanced reactivity of t-BuLi with stoichiometric amounts of THF on the basis of structural features of the bridged dimer obtained under these conditions. With these findings, we present a new target in the aggregation of alkyllithium reagents the selectively formed "frustrated" aggregates!
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Chemistry
Assunto da revista:
QUIMICA
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
Alemanha