Alkynes bearing a stereocenter at the propargylic position are components of biologically active molecules and have served as useful building blocks for stereoselective synthesis (Scheme 1A). Widely applied approaches for their synthesis include the substitution of propargylic alcohol derivatives and the nucleophilic addition of acetylene anion to electrophiles. As an alternative, the enantioselective transformation of propargylic C(sp )-H bonds constitutes a streamlined but underdeveloped approach for obtaining α-functionalized products (Scheme 1B). The radical-based enantioselective Kharasch-Sosnovsky oxygenation represents an early example of such a transformation, though it remains limited in scope and underexplored for alkyne substrates. More recently, Guosheng Liu and coworkers reported a successful radical relay-induced propargylic cyanation based on chiral Cu catalysts, which is also believed to involve radical and organocopper intermediates. Metal nitrene insertion is another powerful tool for C(sp )-H functionalization, and these methods are particularly effective for intramolecular propargylic amination reactions. 4e-i While intermolecular transformations remain rare, enzymatic methods have been successfully applied toward the synthesis of propargylic amines and alcohols. Chiral compounds containing silicon are of significant interest to drug and agrochemical discovery efforts. Enantioenriched organosilicon compounds are also versatile synthetic intermediates that can be transformed stereospecifically into a range of other functionalized products. Although the selective and efficient synthesis of enantioenriched silanes has been achieved through approaches that include olefin addition, 8a-j allylic substitution, 8k,8l cross coupling, 8m-o and carbene insertion reactions, 8p-t the direct construction of stereodefined C(sp 3 )-Si bonds through metal-catalyzed enantioselective C(sp 3 )-H silylation remains underexplored and seldom reported. Known protocols for enantioselective C(sp )-H silylation are, to the best of our knowledge, limited to the intramolecular desymmetrization of substrates bearing pendant cyclopropyl or gem-dimethyl moieties (Scheme 1C). Given the broad availability and accessibility of alkynes and the synthetic versatility of propargylic silanes, we felt that a generally applicable, enantioselective silylation of the α-C-H bonds of alkynes would serve as an attractive, yet thus far unrealized, route to enantioenriched organosilicon compounds. 13