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An Ortho ‐Tetraphenylene‐Based “Geländer” Architecture Consisting Exclusively of 52 sp 2 ‐Hybridized C Atoms
Author(s) -
Dekkiche Hervé,
Malinčik Juraj,
Prescimone Alessandro,
Häussinger Daniel,
Mayor Marcel
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202101968
Subject(s) - enantiomer , biphenyl , molecule , aryl , chemistry , stereochemistry , covalent bond , chiral column chromatography , metathesis , topology (electrical circuits) , olefin fiber , crystallography , catalysis , polymerization , organic chemistry , alkyl , mathematics , combinatorics , polymer
A new type of “Geländer” molecule based on a ortho ‐tetraphenylene core is presented. The central para ‐quaterphenyl backbone is wrapped by a 4,4’‐di(( Z )‐styryl)‐1,1’‐biphenyl banister, with its aryl rings covalently attached to all four phenyl rings of the backbone. The resulting helical chiral bicyclic architecture consists exclusively of sp 2 ‐hybridized carbon atoms. The target structure was assembled by expanding the central ortho ‐tetraphenylene subunit with the required additional phenyl rings followed by a twofold macrocyclization. The first macrocyclization attempts based on a twofold McMurry coupling were successful but low yielding; the second strategy, profiting from olefin metathesis, provided satisfying yields. Hydrogenation of the olefins resulted in a saturated derivative of similar topology, thereby allowing the interdependence between saturation and physico‐chemical properties to be studied. The target structures, including their solid‐state structures, were fully characterized. The helical chiral bicycle was synthesized as a racemate and separated into pure enantiomers by HPLC on a chiral stationary phase. Comparison of recorded and simulated chiroptical properties allowed the enantiomers to be assigned.