From an α-Functionalized Silicon-Stereogenic N,O-Silane to a Monomeric and Tetracoordinate tBuLi Adduct with Lithium-Centered Chirality

Donor-functionalized silanes with stereogenic silicon centers are extremely rare. A convenient stereocontrolled route to a nitrogen-oxygen-functionalized silicon-chiral compound with an additional aminomethyl function is presented. This silane was directly achieved in stereochemically pure form by a simple nucleophilic substitution reaction. Owing to the unique asymmetry of this silane and the presence of three donor functions, the first monomeric butyllithium compound with lithium-centered chirality could be isolated; the configuration was assigned by X-ray crystallography. This [silane tBuLi] complex undergoes an unexpected deprotonation/stereospecific substitution sequence in toluene, leading to the development of a convenient one-pot synthesis of a functionalized silicon-chiral benzylsilane, which proceeds with inversion of configuration and complete preservation of the stereochemical integrity at silicon.