Reaction of Hydrogermanes ArGeH ₃ with Organolithium Reagents RLi: Unexpected Transfer of Organic Groups Instead of Lithiation

A series of novel triorganogermanes featuring an asymmetric germanium center were prepared by the straightforward alkylation of arylhydrogermanes with organolithium reagents (RLi). This synthetic approach represents a step-economical alternative to the traditionally employed procedure based on the quenching of germyllithium derivatives (prepared from the corresponding hydrogermanes) with organohalides. The appropriate choice of reaction solvent, temperature, and organolithium compound enables exclusive (or at least preferential) alkylation/arylation of organogermanium hydrides at the Ge-H bond (with RLi reacting as a nucleophile) at the expense of the traditionally anticipated lithiation of these compounds (with RLi reacting as a base).