Masked Alkyne Equivalents for the Synthesis of Mechanically Interlocked Polyynes*.

Abstract

Polyyne polyrotaxanes, encapsulated cyclocarbon catenanes and other fascinating mechanically interlocked carbon-rich architectures should become accessible if masked alkyne equivalents (MAEs) can be developed that are large enough to prevent unthreading of a macrocycle, and that can be cleanly unmasked under mild conditions. Herein, we report the synthesis of a new bulky MAE based on t-butylbicyclo[4.3.1]decatriene. This MAE was used to synthesize a polyyne [2]rotaxane and a masked-polyyne [3]rotaxane by Cadiot-Chodkiewicz coupling. Glaser cyclo-oligomerization of the [2]rotaxane gave masked cyclocarbon catenanes. The unmasking behavior of the catenanes and rotaxanes was tested by photolysis at a range of UV wavelengths. Photochemical unmasking did not proceed cleanly enough to prepare extended encapsulated polyyne polyrotaxanes. We highlight the scope and challenges involved with this approach to interlocked carbon-rich architectures.