Simple access to highly functional bicyclic γ- and δ-lactams: origins of chirality transfer to contiguous tertiary/quaternary stereocenters assessed by DFT.
Identifieur interne : 000153 ( France/Analysis ); précédent : 000152; suivant : 000154Simple access to highly functional bicyclic γ- and δ-lactams: origins of chirality transfer to contiguous tertiary/quaternary stereocenters assessed by DFT.
Auteurs : Ronan Le Goff [France] ; Arnaud Martel ; Morgane Sanselme ; Ata Martin Lawson ; Adam Daïch ; Sébastien ComesseSource :
- Chemistry (Weinheim an der Bergstrasse, Germany) [ 1521-3765 ] ; 2015.
English descriptors
- KwdEn :
- Bicyclo Compounds, Heterocyclic (chemical synthesis), Bicyclo Compounds, Heterocyclic (chemistry), Hydrogen Bonding, Lactams (chemical synthesis), Lactams (chemistry), Models, Molecular, Molecular Conformation, Oxazoles (chemical synthesis), Oxazoles (chemistry), Piperidines (chemical synthesis), Piperidines (chemistry), Pyrrolidinones (chemical synthesis), Pyrrolidinones (chemistry), Stereoisomerism.
- MESH :
- chemical , chemical synthesis : Bicyclo Compounds, Heterocyclic, Lactams, Oxazoles, Piperidines, Pyrrolidinones.
- chemical , chemistry : Bicyclo Compounds, Heterocyclic, Lactams, Oxazoles, Piperidines, Pyrrolidinones.
- Hydrogen Bonding, Models, Molecular, Molecular Conformation, Stereoisomerism.
Abstract
This paper describes the synthesis of both polysubstituted oxazolo-pyrrolidinones and -piperidinones by a domino process. The methodology is based on the reaction between hydroxyl halogenoamides and Michael acceptors, which leads efficiently to bicyclic lactams. The process is compatible with unsymmetrical electron-withdrawing groups on the Michael acceptor, which allows the formation of two contiguous and fully controlled tertiary and quaternary stereocenters. In the case of tetrasubstituted Michael acceptors, two adjacent quaternary stereocenters are formed in good yield. Starting from (R)-phenylglycinol derived amides results in the formation of enantioenriched bicyclic lactams in low to good yields and with high levels of stereoselectivity, thus greatly increasing the scope and interest of this strategy. The origins of chirality transfer and diastereoselectivity were studied by DFT calculations and have been attributed to a kinetic control in one of the last two steps of the reaction sequence. This selectivity is dependent upon both the substituents on the Michael acceptor and the sodium cation chelation.
DOI: 10.1002/chem.201405094
PubMed: 25524225
Affiliations:
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pubmed:25524225Le document en format XML
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FR CNRS 3038, Université du Havre, UFR Sciences et Techniques, 25 rue Philippe Lebon, 76058 Le Havre cedex (France), Fax: (+033) 2-32-74-43-91.</nlm:affiliation><orgName type="university">Université du Havre</orgName><country>France</country><placeName><settlement type="city">Le Havre</settlement><region type="region" nuts="2">Région Normandie</region><region type="old region" nuts="2">Haute-Normandie</region></placeName></affiliation></author><author><name sortKey="Martel, Arnaud" sort="Martel, Arnaud" uniqKey="Martel A" first="Arnaud" last="Martel">Arnaud Martel</name></author><author><name sortKey="Sanselme, Morgane" sort="Sanselme, Morgane" uniqKey="Sanselme M" first="Morgane" last="Sanselme">Morgane Sanselme</name></author><author><name sortKey="Lawson, Ata Martin" sort="Lawson, Ata Martin" uniqKey="Lawson A" first="Ata Martin" last="Lawson">Ata Martin Lawson</name></author><author><name sortKey="Daich, Adam" sort="Daich, Adam" uniqKey="Daich A" first="Adam" last="Daïch">Adam Daïch</name></author><author><name sortKey="Comesse, Sebastien" sort="Comesse, Sebastien" uniqKey="Comesse S" first="Sébastien" last="Comesse">Sébastien Comesse</name></author></analytic><series><title level="j">Chemistry (Weinheim an der Bergstrasse, Germany)</title><idno type="eISSN">1521-3765</idno><imprint><date when="2015" type="published">2015</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Bicyclo Compounds, Heterocyclic (chemical synthesis)</term><term>Bicyclo Compounds, Heterocyclic (chemistry)</term><term>Hydrogen Bonding</term><term>Lactams (chemical synthesis)</term><term>Lactams (chemistry)</term><term>Models, Molecular</term><term>Molecular Conformation</term><term>Oxazoles (chemical synthesis)</term><term>Oxazoles (chemistry)</term><term>Piperidines (chemical synthesis)</term><term>Piperidines (chemistry)</term><term>Pyrrolidinones (chemical synthesis)</term><term>Pyrrolidinones (chemistry)</term><term>Stereoisomerism</term></keywords><keywords scheme="MESH" type="chemical" qualifier="chemical synthesis" xml:lang="en"><term>Bicyclo Compounds, Heterocyclic</term><term>Lactams</term><term>Oxazoles</term><term>Piperidines</term><term>Pyrrolidinones</term></keywords><keywords scheme="MESH" type="chemical" qualifier="chemistry" xml:lang="en"><term>Bicyclo Compounds, Heterocyclic</term><term>Lactams</term><term>Oxazoles</term><term>Piperidines</term><term>Pyrrolidinones</term></keywords><keywords scheme="MESH" xml:lang="en"><term>Hydrogen Bonding</term><term>Models, Molecular</term><term>Molecular Conformation</term><term>Stereoisomerism</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">This paper describes the synthesis of both polysubstituted oxazolo-pyrrolidinones and -piperidinones by a domino process. The methodology is based on the reaction between hydroxyl halogenoamides and Michael acceptors, which leads efficiently to bicyclic lactams. The process is compatible with unsymmetrical electron-withdrawing groups on the Michael acceptor, which allows the formation of two contiguous and fully controlled tertiary and quaternary stereocenters. In the case of tetrasubstituted Michael acceptors, two adjacent quaternary stereocenters are formed in good yield. Starting from (R)-phenylglycinol derived amides results in the formation of enantioenriched bicyclic lactams in low to good yields and with high levels of stereoselectivity, thus greatly increasing the scope and interest of this strategy. The origins of chirality transfer and diastereoselectivity were studied by DFT calculations and have been attributed to a kinetic control in one of the last two steps of the reaction sequence. This selectivity is dependent upon both the substituents on the Michael acceptor and the sodium cation chelation.</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="Comesse, Sebastien" sort="Comesse, Sebastien" uniqKey="Comesse S" first="Sébastien" last="Comesse">Sébastien Comesse</name><name sortKey="Daich, Adam" sort="Daich, Adam" uniqKey="Daich A" first="Adam" last="Daïch">Adam Daïch</name><name sortKey="Lawson, Ata Martin" sort="Lawson, Ata Martin" uniqKey="Lawson A" first="Ata Martin" last="Lawson">Ata Martin Lawson</name><name sortKey="Martel, Arnaud" sort="Martel, Arnaud" uniqKey="Martel A" first="Arnaud" last="Martel">Arnaud Martel</name><name sortKey="Sanselme, Morgane" sort="Sanselme, Morgane" uniqKey="Sanselme M" first="Morgane" last="Sanselme">Morgane Sanselme</name></noCountry><country name="France"><region name="Région Normandie"><name sortKey="Le Goff, Ronan" sort="Le Goff, Ronan" uniqKey="Le Goff R" first="Ronan" last="Le Goff">Ronan Le Goff</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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