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Synthesis, Structure, and Molecular Recognition of S 6 ‐ and (SO 2 ) 6 ‐Corona[6](het)arenes: Control of Macrocyclic Conformation and Properties by the Oxidation State of the Bridging Heteroatoms
Author(s) -
Guo QingHui,
Zhao Liang,
Wang MeiXiang
Publication year - 2016
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.201600462
Subject(s) - chemistry , dithiol , ring (chemistry) , heteroatom , fluorene , photochemistry , nucleophilic aromatic substitution , thioether , nucleophile , crystallography , stereochemistry , nucleophilic substitution , medicinal chemistry , organic chemistry , catalysis , polymer
We report herein the synthesis, structure, and molecular recognition of S 6 ‐ and (SO 2 ) 6 ‐corona[6](het)arenes, and demonstrate a unique and efficient strategy of regulating macrocyclic conformation and properties by adjusting the oxidation state of the heteroatom linkages. The one‐pot nucleophilic aromatic substitution reaction of 1,4‐benzenedithiol derivatives, biphenyl‐4,4′‐dithiol and 9,9‐dipropyl‐9 H ‐fluorene‐2,7‐dithiol with 3,6‐dichlorotetrazine afforded S 6 ‐corona[3]arene[3]tetrazines. These compounds underwent inverse‐electron‐demand Diels–Alder reaction with enamines and norbornadiene to produce S 6 ‐corona[3]arene[3]pyridazines. Facile oxidation of sulfide linkages yielded (SO 2 ) 6 ‐corona[3]arene[3]pyridazines. All corona[6](het)arenes adopted generally hexagonal macrocyclic ring structures; however, their electronic properties and conformation could be fine‐tuned by altering the oxidation state of the sulfur linkages. Whereas (SO 2 ) 6 ‐corona[3]arene[3]pyridazines were electron‐deficient, S 6 ‐corona[3]arene[3]pyridazines acted as electron‐rich macrocyclic hosts that recognized various organic cations in both aqueous and organic solutions.