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 “Geländer” 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 arou...

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Bibliographic Details
Published in:Chemistry : a European journal 2021-04, Vol.27 (20), p.6295-6307
Main Authors: Bannwart, Linda Maria, Müntener, Thomas, Rickhaus, Michel, Jundt, Lukas, Häussinger, Daniel, Mayor, Marcel
Format: Article
Language:English
Subjects:
Acetylene
Alkynes
Backbone
Benzene
Bridge loads
Chemical synthesis
Chemistry
chirality
Coupling (molecular)
cross-coupling
Hydrocarbons
macrocycles
NMR
Nuclear magnetic resonance
Oligomers
Oxygen
Scaffolding
tropos isomer
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Summary:The novel diacetylene bridged terphenylic macrocycle 1 is presented and discussed in the context of rotationally restricted “Geländer” 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. The conjugated 1,4‐bis(phenylbuta‐1,3‐diyn‐1‐yl) benzene bridge of our terphenylic macrocycle is significantly longer than the backbone it rotates around, thereby forcing itself to bend along the central pylon. The synthesis of the macromolecule is largely based on orthogonal acetylene scaffolding strategies, allowing to sequentially finalize both macrocyclic subunits by oxidative acetylene coupling. The spatial arrangement and the dynamic enantiomerization process of the final, bicyclic compound are analyzed and discussed.
ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.202005207