Bicyclic Phenyl-Ethynyl Architectures: Synthesis of a 1,4-Bis(phenylbuta-1,3-diyn-1-yl) Benzene Banister

The novel diacetylene bridged terphenylic macrocycle 1 is presented and discussed in the context of rotationally restricted "Gelander" oligomers. The 1,4-bis(phenylbuta-1,3-diyn-1-yl) benzene bridge of diacetylene 1 is significantly longer than its terphenyl backbone, forcing the bridge to bend around the central pylon. The synthesis of molecule 1 is based to a large extent on acetylene scaffolding strategies, profiting from orthogonal alkyne protection groups to close both macrocyclic subunits by oxidative acetylene coupling sequentially. The spatial arrangement and the dynamic enantiomerization process of the bicyclic target structure 1 are analyzed. In-depth NMR investigations not only reveal an unexpected spatial arrangement with both oligomer strands bent alongside the backbone, but also display the limited stability of the model compound in the presence of molecular oxygen.