Acetylenes trimethylsilyl cyanide reactions

Two groups simultaneously found that trimethylsilyl cyanide reacts with disubstituted acetylenes in the presence of a Pd catalyst to form silylated 2-amino-5-cyanopyrroles 194 or 195 [133, 134], These reactions are run neat and a variety of Pd species are successful in this transformation [133]. In the case of unsymmetrical diaryl acetylenes, the reaction is not regioselective [134],... 

D. PALLADIUM-CATALYZED REACTION OF TRIMETHYLSILYL CYANIDE WITH ACETYLENE... 

Addition of trimethylsilyl cyanide to carbon-carbon triple bonds proceeds effectively in the presence of palladium catalyst to give cyano-substituted alkenylsilanes in good yields. Reaction of trimethylsilyl iodide with alkynes under the coexistence of acetylenic tin compounds gives three-component coupling products effectively. 

Propargylic Anion Equivalent. (TMS)allene reacts with electrophiles at the C-3 position in an Se2 process analogous to electrophilic substitution reactions of allyl- andpropargylsilanes. For example, upon treatment with trimethylsilyl chlorosulfonate or sulfur trioxide-1,4-dioxane, (TMS)allene yields silyl esters of sulfonic acids (eq 3). (TMS)allene undergoes conjugate addition with a, 8-unsaturated acyl cyanides to yield 5,e-acetylenic acyl cyanides. ... 

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