Abstract Fluorosilanes react with lithium amides and organolithium compounds to give aminofluorosilanes. (Lithioamino)fluorosilanes are formed by the reaction of aminofluorosilanes with butyllithium depending on the steric influence and molecular stabilization of the ligands. These lithium salts react with halogensilanes and trimethyltin chloride with substitution. By LiF elimination the lithioaminofluorosilane C6H5-SiF-NLiC(CH3)3-N(p-C6H4CH3Si(CH3)3) cyclisizes through a (2+2)cycloaddition and SiC-H-cleavage.