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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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">Optically pure calix[6]tris-ammoniums: syntheses and host-guest properties toward neutral guests.</title><author><name sortKey="Darbost, Ulrich" sort="Darbost, Ulrich" uniqKey="Darbost U" first="Ulrich" last="Darbost">Ulrich Darbost</name><affiliation wicri:level="4"><nlm:affiliation>URCOM, Université du Havre, FST, 25 rue Philippe Lebon, BP 540, 76058 Le Havre Cedex, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>URCOM, Université du Havre, FST, 25 rue Philippe Lebon, BP 540, 76058 Le Havre Cedex</wicri:regionArea><placeName><region type="region" nuts="2">Région Normandie</region><region type="old region" nuts="2">Haute-Normandie</region><settlement type="city">Le Havre</settlement></placeName><orgName type="university">Université du Havre</orgName></affiliation></author><author><name sortKey="Zeng, Xianshun" sort="Zeng, Xianshun" uniqKey="Zeng X" first="Xianshun" last="Zeng">Xianshun Zeng</name></author><author><name sortKey="Giorgi, Michel" sort="Giorgi, Michel" uniqKey="Giorgi M" first="Michel" last="Giorgi">Michel Giorgi</name></author><author><name sortKey="Jabin, Ivan" sort="Jabin, Ivan" uniqKey="Jabin I" first="Ivan" last="Jabin">Ivan Jabin</name></author></titleStmt><publicationStmt><idno type="wicri:source">PubMed</idno><date when="2005">2005</date><idno type="RBID">pubmed:16323870</idno><idno type="pmid">16323870</idno><idno type="doi">10.1021/jo051886y</idno><idno type="wicri:Area/PubMed/Corpus">000303</idno><idno type="wicri:Area/PubMed/Curation">000303</idno><idno type="wicri:Area/PubMed/Checkpoint">000303</idno><idno type="wicri:Area/Ncbi/Merge">000135</idno><idno type="wicri:Area/Ncbi/Curation">000135</idno><idno type="wicri:Area/Ncbi/Checkpoint">000135</idno><idno type="wicri:doubleKey">0022-3263:2005:Darbost U:optically:pure:calix</idno><idno type="wicri:Area/Main/Merge">001243</idno><idno type="wicri:Area/Main/Curation">001217</idno><idno type="wicri:Area/Main/Exploration">001217</idno></publicationStmt><sourceDesc><biblStruct><analytic><title xml:lang="en">Optically pure calix[6]tris-ammoniums: syntheses and host-guest properties toward neutral guests.</title><author><name sortKey="Darbost, Ulrich" sort="Darbost, Ulrich" uniqKey="Darbost U" first="Ulrich" last="Darbost">Ulrich Darbost</name><affiliation wicri:level="4"><nlm:affiliation>URCOM, Université du Havre, FST, 25 rue Philippe Lebon, BP 540, 76058 Le Havre Cedex, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>URCOM, Université du Havre, FST, 25 rue Philippe Lebon, BP 540, 76058 Le Havre Cedex</wicri:regionArea><placeName><region type="region" nuts="2">Région Normandie</region><region type="old region" nuts="2">Haute-Normandie</region><settlement type="city">Le Havre</settlement></placeName><orgName type="university">Université du Havre</orgName></affiliation></author><author><name sortKey="Zeng, Xianshun" sort="Zeng, Xianshun" uniqKey="Zeng X" first="Xianshun" last="Zeng">Xianshun Zeng</name></author><author><name sortKey="Giorgi, Michel" sort="Giorgi, Michel" uniqKey="Giorgi M" first="Michel" last="Giorgi">Michel Giorgi</name></author><author><name sortKey="Jabin, Ivan" sort="Jabin, Ivan" uniqKey="Jabin I" first="Ivan" last="Jabin">Ivan Jabin</name></author></analytic><series><title level="j">The Journal of organic chemistry</title><idno type="ISSN">0022-3263</idno><imprint><date when="2005" type="published">2005</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Calixarenes (chemical synthesis)</term><term>Calixarenes (chemistry)</term><term>Magnetic Resonance Spectroscopy</term><term>Molecular Conformation</term><term>Phenols (chemical synthesis)</term><term>Phenols (chemistry)</term><term>Quaternary Ammonium Compounds</term></keywords><keywords scheme="MESH" type="chemical" qualifier="chemical synthesis" xml:lang="en"><term>Calixarenes</term><term>Phenols</term></keywords><keywords scheme="MESH" type="chemical" qualifier="chemistry" xml:lang="en"><term>Calixarenes</term><term>Phenols</term></keywords><keywords scheme="MESH" xml:lang="en"><term>Magnetic Resonance Spectroscopy</term><term>Molecular Conformation</term><term>Quaternary Ammonium Compounds</term></keywords></textClass></profileDesc></teiHeader><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></front></TEI><affiliations><list><country><li>France</li></country><region><li>Haute-Normandie</li><li>Région Normandie</li></region><settlement><li>Le Havre</li></settlement><orgName><li>Université du Havre</li></orgName></list><tree><noCountry><name sortKey="Giorgi, Michel" sort="Giorgi, Michel" uniqKey="Giorgi M" first="Michel" last="Giorgi">Michel Giorgi</name><name sortKey="Jabin, Ivan" sort="Jabin, Ivan" uniqKey="Jabin I" first="Ivan" last="Jabin">Ivan Jabin</name><name sortKey="Zeng, Xianshun" sort="Zeng, Xianshun" uniqKey="Zeng X" first="Xianshun" last="Zeng">Xianshun Zeng</name></noCountry><country name="France"><region name="Région Normandie"><name sortKey="Darbost, Ulrich" sort="Darbost, Ulrich" uniqKey="Darbost U" first="Ulrich" last="Darbost">Ulrich Darbost</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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