Abstract Sulfonating agents such as trimethylsilyl chlorosulfonate and “dioxane, SO 3”, react with silylalkynes (ΣCH 2 C CSiMe 3) in which Σ is a functional group, to yield silylacetylene sulfonates (Σ= OMe, Cl), acetylenic sulfates (Σ= OH, OSiMe 3) or SO 3 nitrogen adduct (Σ= NR 2). Allenoxysilanes Me 3 Si (Σ 1) C C C (Σ 2) OSiMe 3 yield either allenic sulfate (Σ 1= Me 3 Si, Σ 2= t-Bu) or silyl ketonic sulfonate (Σ 1= n-Bu, Σ 2= t-Bu). A mechanism is ...