Synthesis of Diynes and Tetraynes from in Situ Desilylation/Dimerization of Acetylenes

An efficient method for the in situ desilylation/oxidative dimerization of (trialkylsilyl)acetylenes is described. This protocol avoids the complications encountered with sensitive diynes by eliminating the deprotection and isolation steps. Various aromatic and alkyl diynes and tetraynes can be synthesized in a straightforward manner in good yields (82−99%) from TIPS-protected acetylenes. This method facilitates the efficient synthesis of novel tetrayne-bridged acetylenic cyclophanes 6 and 7 in a direct manner.