In summary, we developed a direct enantioselective C(sp 3 )-H silylation at the propargylic position. This method features high enantio-and regioselectivity, and a catalytic cycle is proposed involving attack of silyl triflate reagent by an Ir(I) center based on kinetic and other mechanistic data. Further studies of the detailed mechanism and explorations of additional applications of this strategy toward installation of propargylic stereocenters are ongoing and will be reported in due course. Supporting Information. Experimental procedures, spectroscopic data for the substrates and products (PDF). This material is available free of charge via the Internet at . ym.wang@pitt.edu