Silylative Coupling of Terminal Alkynes with Iodosilanes: New Catalytic Activation of sp-Hybridized Carbon−Hydrogen Bonds

The [{Ir(μ-Cl)(CO)2}2] (I)-catalyzed reaction of terminal alkynes and diynes with Me3SiI with the aid of NEt(i-Pr)2 occurs smoothly, leading to the formation of mono- and bis-silyl-functionalized alkynyl derivatives. This new reaction, which occurs via direct activation of the Csp−H bond in the starting alkyne, is a very efficient and easy tool for the synthesis of unique silylated alkynes. Separate experiments of the equimolar reactions of the precursor (I) with selected reaction substrates provided the evidence for the sequence reactions as well as for the real catalyst to be [IrI(CO)(NEt(i-Pr)2)2].