Efficient synthesis of calix[6]tmpa: a new calix[6]azacryptand with unique conformational and host-guest properties.
Identifieur interne : 000161 ( Ncbi/Checkpoint ); précédent : 000160; suivant : 000162Efficient synthesis of calix[6]tmpa: a new calix[6]azacryptand with unique conformational and host-guest properties.
Auteurs : Xianshun Zeng [France] ; David Coquière ; Aurélie Alenda ; Eva Garrier ; Thierry Prangé ; Yun Li ; Olivia Reinaud ; Ivan JabinSource :
- Chemistry (Weinheim an der Bergstrasse, Germany) [ 0947-6539 ] ; 2006.
Abstract
A new C(3v)-symmetrical calix[6]azacryptand, that is, calix[6]tmpa (11), was synthesized by efficient [1+1] macrocyclization reactions. Remarkably, both linear and convergent synthetic strategies that were applied lead to equally good overall yields. Calix[6]tmpa behaves as a single proton sponge and appeared reluctant to undergo polyprotonation, unlike classical tris(2-pyridylmethyl)amine (tmpa) derivatives. It also acts as a good host for ammonium ions. Interestingly, it strongly binds a sodium ion and a neutral guest molecule, such as a urea, an amide, or an alcohol, in a cooperative way. A (1)H NMR study indicated that the ligand, as well as its complexes, adopt a major flattened cone conformation that is the opposite of that observed with the previously reported calix[6]cryptands. Characterization of the monoprotonated derivative 11H(+) by X-ray diffraction also revealed the presence of a 1,3-alternate conformation, which is the first example of its kind in the calix[6]arene family. This conformer is probably also present in solution as a minor species. The important covalent constraint induced by the polyaromatic tmpa cap on the calixarene skeleton, and conversely from the calix core onto the tmpa moiety, is the likely basis for the unique conformational and chemical properties of this host.
DOI: 10.1002/chem.200600278
PubMed: 16823788
Affiliations:
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Remarkably, both linear and convergent synthetic strategies that were applied lead to equally good overall yields. Calix[6]tmpa behaves as a single proton sponge and appeared reluctant to undergo polyprotonation, unlike classical tris(2-pyridylmethyl)amine (tmpa) derivatives. It also acts as a good host for ammonium ions. Interestingly, it strongly binds a sodium ion and a neutral guest molecule, such as a urea, an amide, or an alcohol, in a cooperative way. A (1)H NMR study indicated that the ligand, as well as its complexes, adopt a major flattened cone conformation that is the opposite of that observed with the previously reported calix[6]cryptands. Characterization of the monoprotonated derivative 11H(+) by X-ray diffraction also revealed the presence of a 1,3-alternate conformation, which is the first example of its kind in the calix[6]arene family. This conformer is probably also present in solution as a minor species. The important covalent constraint induced by the polyaromatic tmpa cap on the calixarene skeleton, and conversely from the calix core onto the tmpa moiety, is the likely basis for the unique conformational and chemical properties of this host.</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="Alenda, Aurelie" sort="Alenda, Aurelie" uniqKey="Alenda A" first="Aurélie" last="Alenda">Aurélie Alenda</name><name sortKey="Coquiere, David" sort="Coquiere, David" uniqKey="Coquiere D" first="David" last="Coquière">David Coquière</name><name sortKey="Garrier, Eva" sort="Garrier, Eva" uniqKey="Garrier E" first="Eva" last="Garrier">Eva Garrier</name><name sortKey="Jabin, Ivan" sort="Jabin, Ivan" uniqKey="Jabin I" first="Ivan" last="Jabin">Ivan Jabin</name><name sortKey="Li, Yun" sort="Li, Yun" uniqKey="Li Y" first="Yun" last="Li">Yun Li</name><name sortKey="Prange, Thierry" sort="Prange, Thierry" uniqKey="Prange T" first="Thierry" last="Prangé">Thierry Prangé</name><name sortKey="Reinaud, Olivia" sort="Reinaud, Olivia" uniqKey="Reinaud O" first="Olivia" last="Reinaud">Olivia Reinaud</name></noCountry><country name="France"><region name="Région Normandie"><name sortKey="Zeng, Xianshun" sort="Zeng, Xianshun" uniqKey="Zeng X" first="Xianshun" last="Zeng">Xianshun Zeng</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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