Generation of Stereocenters Around a C3‐Symmetric Cyclotriveratrylene Crown
Identifieur interne : 001E30 ( Main/Exploration ); précédent : 001E29; suivant : 001E31Generation of Stereocenters Around a C3‐Symmetric Cyclotriveratrylene Crown
Auteurs : Julien Sansévérino ; Emmanuel Aubert [France] ; Enrique Espinosa [France] ; Jean-Claude Chambron [France]Source :
- European Journal of Organic Chemistry [ 1434-193X ] ; 2012-04.
English descriptors
- Teeft :
- Asymmetric diastereomers, Asymmetric isomers, Benzene ring, Camphoryl backbone, Cdcl3, Chem, Chemical shifts, Chiral, Chirality, Chloroform medium, Collet, Column chromatography, Crude reaction mixture, Cyclotriveratrylene, Derivative, Diastereomer, Diastereomeric, Diastereomeric pairs, Diastereomeric ratios, Diastereomers, Enantiomeric pair, Flash column chromatography, Institut jean barriol, Isomer, Major diastereomer, Methyl, Methyl sulfinyl protons, Mmol, Negligible role, Other diastereomers, Oxaziridine, Oxygen atom, Perkin trans, Proton, Reaction mixture, Results point, Room temperature, Singlet, Small amounts, Spectroscopic analysis, Spectroscopic data, Stereocenters, Stereochemical course, Stereochemical outcome, Sulfinyl, Sulfinyl methyl protons, Sulfoxidation, Sulfoxidation reaction, Sulfur prochiral centers, Verlag gmbh.
Abstract
The oxidation of racemic methylthio‐substituted C3‐symmetric cyclotriveratrylene (CTV) 2 produces the corresponding trisulfoxides 3 as follows. Oxidation with m‐chloroperoxybenzoic acid (m‐CPBA) in dichloromethane leads to the formation of a distribution of the four possible diastereomers that is relatively close to the statistical outcome, in which the C3‐symmetric stereoisomers are the minor species. In contrast, the optically active Davis reagent [oxaziridine (+)‐4] in carbon tetrachloride at room temperature leads to a biased (73 %) distribution in favor of the C3‐symmetric MRRR/PSSS diastereomer of 3 with 56 % ee (PSSS enantiomer according to the model of Davis). Interestingly, when the oxidation is carried out in toluene at reflux, the distribution is switched to approximately equal amounts of the C3‐symmetric MSSS/PRRR and asymmetric MRSS/PSRR diastereomers of 3. Overall, however, these results point to the negligible role played by the chirality of the CTV platform on the induction of chirality at the sulfur prochiral centers.
Sulfoxidation of racemic cyclotriveratrylene 2 can produce up to four diastereomeric pairs of enantiomers. Whereas m‐CPBA‐mediated oxidation affords a mixture of diastereoisomers with a statistical distribution (which favors asymmetrical species), optically active oxaziridine (+)‐4 produces mainly (73 %) the C3‐symmetric diastereomeric pair MRRR/PSSS‐3 with an enantiomeric ratio of 22:78 in CCl4.
Url:
DOI: 10.1002/ejoc.201101780
Affiliations:
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sort="Sanseverino, Julien" uniqKey="Sanseverino J" first="Julien" last="Sansévérino">Julien Sansévérino</name><affiliation><wicri:noCountry code="subField">+33‐3‐80396117</wicri:noCountry></affiliation></author><author><name sortKey="Aubert, Emmanuel" sort="Aubert, Emmanuel" uniqKey="Aubert E" first="Emmanuel" last="Aubert">Emmanuel Aubert</name><affiliation wicri:level="3"><country xml:lang="fr">France</country><wicri:regionArea>CRM2 (CNRS UMR no. 7036), Institut Jean Barriol, Faculté des Sciences et Technologies, Nancy‐Université, Boulevard des Aiguillettes, BP 70239, 54506 Vandœuvre‐lès‐Nancy</wicri:regionArea><placeName><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Lorraine (région)</region><settlement type="city">Vandœuvre‐lès‐Nancy</settlement></placeName></affiliation></author><author><name sortKey="Espinosa, Enrique" sort="Espinosa, Enrique" uniqKey="Espinosa E" first="Enrique" last="Espinosa">Enrique Espinosa</name><affiliation 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mixture</term><term>Cyclotriveratrylene</term><term>Derivative</term><term>Diastereomer</term><term>Diastereomeric</term><term>Diastereomeric pairs</term><term>Diastereomeric ratios</term><term>Diastereomers</term><term>Enantiomeric pair</term><term>Flash column chromatography</term><term>Institut jean barriol</term><term>Isomer</term><term>Major diastereomer</term><term>Methyl</term><term>Methyl sulfinyl protons</term><term>Mmol</term><term>Negligible role</term><term>Other diastereomers</term><term>Oxaziridine</term><term>Oxygen atom</term><term>Perkin trans</term><term>Proton</term><term>Reaction mixture</term><term>Results point</term><term>Room temperature</term><term>Singlet</term><term>Small amounts</term><term>Spectroscopic analysis</term><term>Spectroscopic data</term><term>Stereocenters</term><term>Stereochemical course</term><term>Stereochemical outcome</term><term>Sulfinyl</term><term>Sulfinyl methyl protons</term><term>Sulfoxidation</term><term>Sulfoxidation reaction</term><term>Sulfur prochiral centers</term><term>Verlag gmbh</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract">The oxidation of racemic methylthio‐substituted C3‐symmetric cyclotriveratrylene (CTV) 2 produces the corresponding trisulfoxides 3 as follows. Oxidation with m‐chloroperoxybenzoic acid (m‐CPBA) in dichloromethane leads to the formation of a distribution of the four possible diastereomers that is relatively close to the statistical outcome, in which the C3‐symmetric stereoisomers are the minor species. In contrast, the optically active Davis reagent [oxaziridine (+)‐4] in carbon tetrachloride at room temperature leads to a biased (73 %) distribution in favor of the C3‐symmetric MRRR/PSSS diastereomer of 3 with 56 % ee (PSSS enantiomer according to the model of Davis). Interestingly, when the oxidation is carried out in toluene at reflux, the distribution is switched to approximately equal amounts of the C3‐symmetric MSSS/PRRR and asymmetric MRSS/PSRR diastereomers of 3. Overall, however, these results point to the negligible role played by the chirality of the CTV platform on the induction of chirality at the sulfur prochiral centers.</div><div type="abstract">Sulfoxidation of racemic cyclotriveratrylene 2 can produce up to four diastereomeric pairs of enantiomers. Whereas m‐CPBA‐mediated oxidation affords a mixture of diastereoisomers with a statistical distribution (which favors asymmetrical species), optically active oxaziridine (+)‐4 produces mainly (73 %) the C3‐symmetric diastereomeric pair MRRR/PSSS‐3 with an enantiomeric ratio of 22:78 in CCl4.</div></front></TEI><affiliations><list><country><li>France</li></country><region><li>Grand Est</li><li>Lorraine (région)</li></region><settlement><li>Vandœuvre‐lès‐Nancy</li></settlement></list><tree><noCountry><name sortKey="Sanseverino, Julien" sort="Sanseverino, Julien" uniqKey="Sanseverino J" first="Julien" last="Sansévérino">Julien Sansévérino</name></noCountry><country name="France"><region name="Grand Est"><name sortKey="Aubert, Emmanuel" sort="Aubert, Emmanuel" uniqKey="Aubert E" first="Emmanuel" last="Aubert">Emmanuel Aubert</name></region><name sortKey="Chambron, Jean Laude" sort="Chambron, Jean Laude" uniqKey="Chambron J" first="Jean-Claude" last="Chambron">Jean-Claude Chambron</name><name sortKey="Chambron, Jean Laude" sort="Chambron, Jean Laude" uniqKey="Chambron J" first="Jean-Claude" last="Chambron">Jean-Claude Chambron</name><name sortKey="Espinosa, Enrique" sort="Espinosa, Enrique" uniqKey="Espinosa E" first="Enrique" last="Espinosa">Enrique Espinosa</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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