Carboxylate catalyzed silylation of 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 p-substituted 2-arylalkynes is consistent with the proposed catalytic cycle involving turnover-determining deprotonation step.