Carboxylate-Catalyzed C -Silylation of Terminal Alkynes.

A carboxylate-catalyzed, metal-free C -silylation protocol for terminal alkynes is reported using a quaternary ammonium pivalate as the catalyst and commercially available N , O -bis(silyl)acetamides as silylating agents. The reaction proceeds under mild conditions, tolerates a range of functionalities, and enables concomitant O - or N -silylation of acidic OH or NH groups. A Hammett ρ value of +1.4 ± 0.1 obtained for para -substituted 2-arylalkynes is consistent with the proposed catalytic cycle involving a turnover-determining deprotonation step.