Syntheses and Structures of Isomeric [6.6]- and [8.8]Cyclophanes with 1,4-Dioxabut-2-yne and 1,6-Dioxahexa-2,4-diyne Bridges^†

All three isomers (<i>ortho</i>, <i>meta</i>, and <i>para</i>) of [8.8]cyclophane bearing 1,6-dioxahexa-2,4-diyne bridges have been synthesized and structually characterized by single-crystal X-ray crystallography to determine the conformation of the cyclophanes and their cavity dimensions. The three isomeric [6.6]cyclophanes bearing 1,4-dioxabut-2-yne bridges have also been synthesized from but-2-yne-1,4-diol ditosylate and the isomeric dihydroxybenzenes. The [6.6]orthocyclophane has been structurally characterized by single-crystal X-ray crystallography. The energy-minimized structures from the semiempirical AM1 calculations of these cyclophanes compare very well with the structures obtained by X-ray crystallography.