Optically pure calix[6]tris-ammoniums: syntheses and host-guest properties toward neutral guests.
Identifieur interne : 001217 ( Main/Exploration ); précédent : 001216; suivant : 001218Optically pure calix[6]tris-ammoniums: syntheses and host-guest properties toward neutral guests.
Auteurs : Ulrich Darbost [France] ; Xianshun Zeng ; Michel Giorgi ; Ivan JabinSource :
- The Journal of organic chemistry [ 0022-3263 ] ; 2005.
English descriptors
- KwdEn :
- MESH :
- chemical , chemical synthesis : Calixarenes, Phenols.
- chemical , chemistry : Calixarenes, Phenols.
- Magnetic Resonance Spectroscopy, Molecular Conformation, Quaternary Ammonium Compounds.
Abstract
[reaction: see text] Optically pure calix[6]arenes bearing chiral amino arms 4, 7, and 10 have been synthesized in high yields from the known symmetrically 1,3,5-trismethylated calix[6]arene. For both compounds 7 and 10, the key step consists of an efficient selective alkylation on the narrow rim of the calix[6]arene with Ba(OH)2 as the base. All of these chiral calix[6]tris-amines possess a similar flattened cone conformation with the cavity occupied by the methoxy groups. In contrast to 4 and 7, upon protonation, the enantiopure calix[6]arene 10 can switch to the opposite flattened cone conformation through self-assembly of its ammonium arms in an ion-paired cap which closes the cavity. As shown by NMR host-guest studies and an X-ray structure, the obtained polarized host (10 x 3H+) behaves as a remarkable endo-receptor for small polar neutral molecules. Thanks to the tris-cationic chiral binding site of 10 x 3H+, it was shown that the guests experience a chiral environment upon inclusion. Finally, the first example of enantioselective molecular recognition inside the cavity of a calix[6]arene has been evidenced with a racemic 1,2-diol guest.
DOI: 10.1021/jo051886y
PubMed: 16323870
Affiliations:
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Le document en format XML
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<front><div type="abstract" xml:lang="en">[reaction: see text] Optically pure calix[6]arenes bearing chiral amino arms 4, 7, and 10 have been synthesized in high yields from the known symmetrically 1,3,5-trismethylated calix[6]arene. For both compounds 7 and 10, the key step consists of an efficient selective alkylation on the narrow rim of the calix[6]arene with Ba(OH)2 as the base. All of these chiral calix[6]tris-amines possess a similar flattened cone conformation with the cavity occupied by the methoxy groups. In contrast to 4 and 7, upon protonation, the enantiopure calix[6]arene 10 can switch to the opposite flattened cone conformation through self-assembly of its ammonium arms in an ion-paired cap which closes the cavity. As shown by NMR host-guest studies and an X-ray structure, the obtained polarized host (10 x 3H+) behaves as a remarkable endo-receptor for small polar neutral molecules. Thanks to the tris-cationic chiral binding site of 10 x 3H+, it was shown that the guests experience a chiral environment upon inclusion. Finally, the first example of enantioselective molecular recognition inside the cavity of a calix[6]arene has been evidenced with a racemic 1,2-diol guest.</div>
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