THF-solvated Heavy Alkali Metal Benzyl Compounds (Na, Rb, Cs): Defined Deprotonation Reagents for Alkali Metal Mediation Chemistry

The incorporation of heavy alkali metals into substrates is both challenging and essential for many reactions. Here, we report the formation of THF-solvated alkali metal benzyl compounds [PhCH2M . (thf)(n)] (M=Na, Rb, Cs). The synthesis was carried out by deprotonation of toluene with the bimetallic mixture n-butyllithium/alkali metal tert-butoxide and selective crystallization from THF of the defined benzyl compounds. Insights into the molecular structure in the solid as well as in solution state are gained by single crystal X-ray experiments and NMR spectroscopic studies. The compounds could be successfully used as alkali metal mediating reagents. The example of caesium showed the convenient use by deprotonating acidic C-H as well as N-H compounds to gain insight into the aminometalation using these reagents.

Automated summary

The formation of THF-solvated alkali metal benzyl compounds [PhCH2M . (thf)(n)] (M=Na, Rb, Cs) was successfully achieved through deprotonation of toluene with a bimetallic mixture and selective crystallization. These compounds can serve as alkali metal mediating reagents and have shown to be convenient for deprotonating acidic C-H as well as N-H compounds for aminometalation.