Efficient Synthesis of Calix[6]tmpa: A New Calix[6]azacryptand with Unique Conformational and Host–Guest Properties
Identifieur interne : 001119 ( Main/Exploration ); précédent : 001118; suivant : 001120Efficient Synthesis of Calix[6]tmpa: A New Calix[6]azacryptand with Unique Conformational and Host–Guest Properties
Auteurs : Xianshun Zeng ; David Coquière ; Aurélie Alenda ; Eva Garrier ; Thierry Prangé [France] ; Yun Li ; Olivia Reinaud [France] ; Ivan Jabin [France]Source :
- Chemistry – A European Journal [ 0947-6539 ] ; 2006-08-16.
English descriptors
Abstract
A new C3v‐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 1H 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 11⋅H+ 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.
Url:
DOI: 10.1002/chem.200600278
Affiliations:
Links toward previous steps (curation, corpus...)
- to stream Istex, to step Corpus: 000A59
- to stream Istex, to step Curation: 000A59
- to stream Istex, to step Checkpoint: 000515
- to stream PubMed, to step Corpus: 000287
- to stream PubMed, to step Curation: 000287
- to stream PubMed, to step Checkpoint: 000287
- to stream Ncbi, to step Merge: 000161
- to stream Ncbi, to step Curation: 000161
- to stream Ncbi, to step Checkpoint: 000161
- to stream Main, to step Merge: 001141
- to stream Main, to step Curation: 001119
Le document en format XML
<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title xml:lang="en">Efficient Synthesis of Calix[6]tmpa: A New Calix[6]azacryptand with Unique Conformational and Host–Guest Properties</title><author><name sortKey="Zeng, Xianshun" sort="Zeng, Xianshun" uniqKey="Zeng X" first="Xianshun" last="Zeng">Xianshun Zeng</name></author><author><name sortKey="Coquiere, David" sort="Coquiere, David" uniqKey="Coquiere D" first="David" last="Coquière">David Coquière</name></author><author><name sortKey="Alenda, Aurelie" sort="Alenda, Aurelie" uniqKey="Alenda A" first="Aurélie" last="Alenda">Aurélie Alenda</name></author><author><name sortKey="Garrier, Eva" sort="Garrier, Eva" uniqKey="Garrier E" first="Eva" last="Garrier">Eva Garrier</name></author><author><name sortKey="Prange, Thierry" sort="Prange, Thierry" uniqKey="Prange T" first="Thierry" last="Prangé">Thierry Prangé</name></author><author><name sortKey="Li, Yun" sort="Li, Yun" uniqKey="Li Y" first="Yun" last="Li">Yun Li</name></author><author><name sortKey="Reinaud, Olivia" sort="Reinaud, Olivia" uniqKey="Reinaud O" first="Olivia" last="Reinaud">Olivia Reinaud</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">ISTEX</idno><idno type="RBID">ISTEX:276E5A53B355F5C51DCF91BFC515DB9A6B6EAB97</idno><date when="2006" year="2006">2006</date><idno type="doi">10.1002/chem.200600278</idno><idno type="url">https://api.istex.fr/document/276E5A53B355F5C51DCF91BFC515DB9A6B6EAB97/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">000A59</idno><idno type="wicri:Area/Istex/Curation">000A59</idno><idno type="wicri:Area/Istex/Checkpoint">000515</idno><idno type="wicri:doubleKey">0947-6539:2006:Zeng X:efficient:synthesis:of</idno><idno type="wicri:source">PubMed</idno><idno type="RBID">pubmed:16823788</idno><idno type="wicri:Area/PubMed/Corpus">000287</idno><idno type="wicri:Area/PubMed/Curation">000287</idno><idno type="wicri:Area/PubMed/Checkpoint">000287</idno><idno type="wicri:Area/Ncbi/Merge">000161</idno><idno type="wicri:Area/Ncbi/Curation">000161</idno><idno type="wicri:Area/Ncbi/Checkpoint">000161</idno><idno type="wicri:doubleKey">0947-6539:2006:Zeng X:efficient:synthesis:of</idno><idno type="wicri:Area/Main/Merge">001141</idno><idno type="wicri:Area/Main/Curation">001119</idno><idno type="wicri:Area/Main/Exploration">001119</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a" type="main" xml:lang="en">Efficient Synthesis of Calix[6]tmpa: A New Calix[6]azacryptand with Unique Conformational and Host–Guest Properties</title><author><name sortKey="Zeng, Xianshun" sort="Zeng, Xianshun" uniqKey="Zeng X" first="Xianshun" last="Zeng">Xianshun Zeng</name><affiliation><wicri:noCountry code="subField">(+33) 232‐744‐391</wicri:noCountry></affiliation></author><author><name sortKey="Coquiere, David" sort="Coquiere, David" uniqKey="Coquiere D" first="David" last="Coquière">David Coquière</name><affiliation><wicri:noCountry code="subField">(+33) 142‐862‐183</wicri:noCountry></affiliation></author><author><name sortKey="Alenda, Aurelie" sort="Alenda, Aurelie" uniqKey="Alenda A" first="Aurélie" last="Alenda">Aurélie Alenda</name><affiliation><wicri:noCountry code="subField">(+33) 142‐862‐183</wicri:noCountry></affiliation></author><author><name sortKey="Garrier, Eva" sort="Garrier, Eva" uniqKey="Garrier E" first="Eva" last="Garrier">Eva Garrier</name><affiliation><wicri:noCountry code="subField">(+33) 232‐744‐391</wicri:noCountry></affiliation></author><author><name sortKey="Prange, Thierry" sort="Prange, Thierry" uniqKey="Prange T" first="Thierry" last="Prangé">Thierry Prangé</name><affiliation wicri:level="3"><country xml:lang="fr">France</country><wicri:regionArea>Laboratoire de Cristallographie et RMN Biologiques, UMR CNRS 8015, Université René Descartes, 4 avenue de l'Observatoire, 75270 Paris Cedex 06</wicri:regionArea><placeName><region type="region" nuts="2">Île-de-France</region><settlement type="city">Paris</settlement></placeName></affiliation></author><author><name sortKey="Li, Yun" sort="Li, Yun" uniqKey="Li Y" first="Yun" last="Li">Yun Li</name><affiliation><wicri:noCountry code="subField">(+33) 142‐862‐183</wicri:noCountry></affiliation></author><author><name sortKey="Reinaud, Olivia" sort="Reinaud, Olivia" uniqKey="Reinaud O" first="Olivia" last="Reinaud">Olivia Reinaud</name><affiliation></affiliation><affiliation wicri:level="1"><country wicri:rule="url">France</country></affiliation></author><author><name sortKey="Jabin, Ivan" sort="Jabin, Ivan" uniqKey="Jabin I" first="Ivan" last="Jabin">Ivan Jabin</name><affiliation></affiliation><affiliation wicri:level="1"><country wicri:rule="url">France</country></affiliation></author></analytic><monogr></monogr><series><title level="j">Chemistry – A European Journal</title><title level="j" type="abbrev">Chemistry – A European Journal</title><idno type="ISSN">0947-6539</idno><idno type="eISSN">1521-3765</idno><imprint><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2006-08-16">2006-08-16</date><biblScope unit="volume">12</biblScope><biblScope unit="issue">24</biblScope><biblScope unit="page" from="6393">6393</biblScope><biblScope unit="page" to="6402">6402</biblScope></imprint><idno type="ISSN">0947-6539</idno></series><idno type="istex">276E5A53B355F5C51DCF91BFC515DB9A6B6EAB97</idno><idno type="DOI">10.1002/chem.200600278</idno><idno type="ArticleID">CHEM200600278</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0947-6539</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>calixarenes</term><term>cryptands</term><term>host–guest systems</term><term>supramolecular chemistry</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract">A new C3v‐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 1H 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 11⋅H+ 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>Île-de-France</li></region><settlement><li>Paris</li></settlement></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="Li, Yun" sort="Li, Yun" uniqKey="Li Y" first="Yun" last="Li">Yun Li</name><name sortKey="Zeng, Xianshun" sort="Zeng, Xianshun" uniqKey="Zeng X" first="Xianshun" last="Zeng">Xianshun Zeng</name></noCountry><country name="France"><region name="Île-de-France"><name sortKey="Prange, Thierry" sort="Prange, Thierry" uniqKey="Prange T" first="Thierry" last="Prangé">Thierry Prangé</name></region><name sortKey="Jabin, Ivan" sort="Jabin, Ivan" uniqKey="Jabin I" first="Ivan" last="Jabin">Ivan Jabin</name><name sortKey="Reinaud, Olivia" sort="Reinaud, Olivia" uniqKey="Reinaud O" first="Olivia" last="Reinaud">Olivia Reinaud</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Wicri/France/explor/LeHavreV1/Data/Main/Exploration
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 001119 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/Main/Exploration/biblio.hfd -nk 001119 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien
|wiki= Wicri/France
|area= LeHavreV1
|flux= Main
|étape= Exploration
|type= RBID
|clé= ISTEX:276E5A53B355F5C51DCF91BFC515DB9A6B6EAB97
|texte= Efficient Synthesis of Calix[6]tmpa: A New Calix[6]azacryptand with Unique Conformational and Host–Guest Properties
}}
| This area was generated with Dilib version V0.6.25. |  |