Asymmetric Sequential Cu-Catalyzed 1,6/1,4-Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity.
Identifieur interne : 000B43 ( PubMed/Curation ); précédent : 000B42; suivant : 000B44Asymmetric Sequential Cu-Catalyzed 1,6/1,4-Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity.
Auteurs : Charlie Blons [France] ; Marie S T. Morin [France] ; Thibault E. Schmid [France] ; Thomas Vives [France] ; Sophie Colombel-Rouen [France] ; Olivier Baslé [France] ; Thibault Reynaldo [France] ; Cody L. Covington [États-Unis] ; Stéphanie Halbert [France] ; Sean N. Cuskelly [Australie] ; Paul V. Bernhardt [Australie] ; Craig M. Williams [Australie] ; Jeanne Crassous [France] ; Prasad L. Polavarapu [États-Unis] ; Christophe Crévisy [France] ; Hélène Gérard [France] ; Marc Mauduit [France]Source :
- Chemistry (Weinheim an der Bergstrasse, Germany) [ 1521-3765 ] ; 2017.
Abstract
The first stereocontrolled Cu-catalyzed sequential 1,6/1,4-asymmetric conjugate addition (ACA) of C-metalated hard nucleophiles to cyclic dienones is reported. The use of DiPPAM (diphenylphosphinoazomethinylate) followed by a phosphoramidite as the stereoinducing ligands facilitated both high ee values for the 1,6-ACA and high de values for the 1,4-ACA reaction components, which thus gave enantioenriched 1,3-dialkylated moieties. The absolute configurations were determined by using vibrational circular dichroism (VCD) and optical rotatory dispersion (ORD) spectroscopy, in combination with DFT calculations and X-ray analysis. Interestingly, DFT calculations for the mechanism of enantioselective 1,6-addition by using an unprecedented Cu-Zn bimetallic catalytic system confirmed this attribution. Lastly, exploring intramolecular cyclization avenues for enantioenriched 1,3-dialkylated products provided access to the challenging drimane skeleton.
DOI: 10.1002/chem.201606034
PubMed: 28370488
Links toward previous steps (curation, corpus...)
- to stream PubMed, to step Corpus: Pour aller vers cette notice dans l'étape Curation :000B46
Links to Exploration step
pubmed:28370488Le document en format XML
<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">Asymmetric Sequential Cu-Catalyzed 1,6/1,4-Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity.</title><author><name sortKey="Blons, Charlie" sort="Blons, Charlie" uniqKey="Blons C" first="Charlie" last="Blons">Charlie Blons</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Morin, Marie S T" sort="Morin, Marie S T" uniqKey="Morin M" first="Marie S T" last="Morin">Marie S T. Morin</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Schmid, Thibault E" sort="Schmid, Thibault E" uniqKey="Schmid T" first="Thibault E" last="Schmid">Thibault E. Schmid</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Vives, Thomas" sort="Vives, Thomas" uniqKey="Vives T" first="Thomas" last="Vives">Thomas Vives</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Colombel Rouen, Sophie" sort="Colombel Rouen, Sophie" uniqKey="Colombel Rouen S" first="Sophie" last="Colombel-Rouen">Sophie Colombel-Rouen</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Basle, Olivier" sort="Basle, Olivier" uniqKey="Basle O" first="Olivier" last="Baslé">Olivier Baslé</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Reynaldo, Thibault" sort="Reynaldo, Thibault" uniqKey="Reynaldo T" first="Thibault" last="Reynaldo">Thibault Reynaldo</name><affiliation wicri:level="1"><nlm:affiliation>Université de Rennes 1, CNRS, UMR 6226, Campus de Beaulieu, 35042, Rennes Cedex, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Université de Rennes 1, CNRS, UMR 6226, Campus de Beaulieu, 35042, Rennes Cedex</wicri:regionArea></affiliation></author><author><name sortKey="Covington, Cody L" sort="Covington, Cody L" uniqKey="Covington C" first="Cody L" last="Covington">Cody L. Covington</name><affiliation wicri:level="1"><nlm:affiliation>Department of Chemistry, Vanderbilt University, Nashville, TN, 37235, USA.</nlm:affiliation><country xml:lang="fr">États-Unis</country><wicri:regionArea>Department of Chemistry, Vanderbilt University, Nashville, TN, 37235</wicri:regionArea></affiliation></author><author><name sortKey="Halbert, Stephanie" sort="Halbert, Stephanie" uniqKey="Halbert S" first="Stéphanie" last="Halbert">Stéphanie Halbert</name><affiliation wicri:level="1"><nlm:affiliation>Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire de Chimie Théorique CC 137, 4, place Jussieu F., 75252, Paris Cedex 05, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire de Chimie Théorique CC 137, 4, place Jussieu F., 75252, Paris Cedex 05</wicri:regionArea></affiliation></author><author><name sortKey="Cuskelly, Sean N" sort="Cuskelly, Sean N" uniqKey="Cuskelly S" first="Sean N" last="Cuskelly">Sean N. Cuskelly</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072, Australia.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072</wicri:regionArea></affiliation></author><author><name sortKey="Bernhardt, Paul V" sort="Bernhardt, Paul V" uniqKey="Bernhardt P" first="Paul V" last="Bernhardt">Paul V. Bernhardt</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072, Australia.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072</wicri:regionArea></affiliation></author><author><name sortKey="Williams, Craig M" sort="Williams, Craig M" uniqKey="Williams C" first="Craig M" last="Williams">Craig M. Williams</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072, Australia.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072</wicri:regionArea></affiliation></author><author><name sortKey="Crassous, Jeanne" sort="Crassous, Jeanne" uniqKey="Crassous J" first="Jeanne" last="Crassous">Jeanne Crassous</name><affiliation wicri:level="1"><nlm:affiliation>Université de Rennes 1, CNRS, UMR 6226, Campus de Beaulieu, 35042, Rennes Cedex, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Université de Rennes 1, CNRS, UMR 6226, Campus de Beaulieu, 35042, Rennes Cedex</wicri:regionArea></affiliation></author><author><name sortKey="Polavarapu, Prasad L" sort="Polavarapu, Prasad L" uniqKey="Polavarapu P" first="Prasad L" last="Polavarapu">Prasad L. Polavarapu</name><affiliation wicri:level="1"><nlm:affiliation>Department of Chemistry, Vanderbilt University, Nashville, TN, 37235, USA.</nlm:affiliation><country xml:lang="fr">États-Unis</country><wicri:regionArea>Department of Chemistry, Vanderbilt University, Nashville, TN, 37235</wicri:regionArea></affiliation></author><author><name sortKey="Crevisy, Christophe" sort="Crevisy, Christophe" uniqKey="Crevisy C" first="Christophe" last="Crévisy">Christophe Crévisy</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Gerard, Helene" sort="Gerard, Helene" uniqKey="Gerard H" first="Hélène" last="Gérard">Hélène Gérard</name><affiliation wicri:level="1"><nlm:affiliation>Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire de Chimie Théorique CC 137, 4, place Jussieu F., 75252, Paris Cedex 05, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire de Chimie Théorique CC 137, 4, place Jussieu F., 75252, Paris Cedex 05</wicri:regionArea></affiliation></author><author><name sortKey="Mauduit, Marc" sort="Mauduit, Marc" uniqKey="Mauduit M" first="Marc" last="Mauduit">Marc Mauduit</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">PubMed</idno><date when="2017">2017</date><idno type="RBID">pubmed:28370488</idno><idno type="pmid">28370488</idno><idno type="doi">10.1002/chem.201606034</idno><idno type="wicri:Area/PubMed/Corpus">000B46</idno><idno type="wicri:explorRef" wicri:stream="PubMed" wicri:step="Corpus" wicri:corpus="PubMed">000B46</idno><idno type="wicri:Area/PubMed/Curation">000B43</idno><idno type="wicri:explorRef" wicri:stream="PubMed" wicri:step="Curation">000B43</idno></publicationStmt><sourceDesc><biblStruct><analytic><title xml:lang="en">Asymmetric Sequential Cu-Catalyzed 1,6/1,4-Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity.</title><author><name sortKey="Blons, Charlie" sort="Blons, Charlie" uniqKey="Blons C" first="Charlie" last="Blons">Charlie Blons</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Morin, Marie S T" sort="Morin, Marie S T" uniqKey="Morin M" first="Marie S T" last="Morin">Marie S T. Morin</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Schmid, Thibault E" sort="Schmid, Thibault E" uniqKey="Schmid T" first="Thibault E" last="Schmid">Thibault E. Schmid</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Vives, Thomas" sort="Vives, Thomas" uniqKey="Vives T" first="Thomas" last="Vives">Thomas Vives</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Colombel Rouen, Sophie" sort="Colombel Rouen, Sophie" uniqKey="Colombel Rouen S" first="Sophie" last="Colombel-Rouen">Sophie Colombel-Rouen</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Basle, Olivier" sort="Basle, Olivier" uniqKey="Basle O" first="Olivier" last="Baslé">Olivier Baslé</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Reynaldo, Thibault" sort="Reynaldo, Thibault" uniqKey="Reynaldo T" first="Thibault" last="Reynaldo">Thibault Reynaldo</name><affiliation wicri:level="1"><nlm:affiliation>Université de Rennes 1, CNRS, UMR 6226, Campus de Beaulieu, 35042, Rennes Cedex, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Université de Rennes 1, CNRS, UMR 6226, Campus de Beaulieu, 35042, Rennes Cedex</wicri:regionArea></affiliation></author><author><name sortKey="Covington, Cody L" sort="Covington, Cody L" uniqKey="Covington C" first="Cody L" last="Covington">Cody L. Covington</name><affiliation wicri:level="1"><nlm:affiliation>Department of Chemistry, Vanderbilt University, Nashville, TN, 37235, USA.</nlm:affiliation><country xml:lang="fr">États-Unis</country><wicri:regionArea>Department of Chemistry, Vanderbilt University, Nashville, TN, 37235</wicri:regionArea></affiliation></author><author><name sortKey="Halbert, Stephanie" sort="Halbert, Stephanie" uniqKey="Halbert S" first="Stéphanie" last="Halbert">Stéphanie Halbert</name><affiliation wicri:level="1"><nlm:affiliation>Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire de Chimie Théorique CC 137, 4, place Jussieu F., 75252, Paris Cedex 05, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire de Chimie Théorique CC 137, 4, place Jussieu F., 75252, Paris Cedex 05</wicri:regionArea></affiliation></author><author><name sortKey="Cuskelly, Sean N" sort="Cuskelly, Sean N" uniqKey="Cuskelly S" first="Sean N" last="Cuskelly">Sean N. Cuskelly</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072, Australia.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072</wicri:regionArea></affiliation></author><author><name sortKey="Bernhardt, Paul V" sort="Bernhardt, Paul V" uniqKey="Bernhardt P" first="Paul V" last="Bernhardt">Paul V. Bernhardt</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072, Australia.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072</wicri:regionArea></affiliation></author><author><name sortKey="Williams, Craig M" sort="Williams, Craig M" uniqKey="Williams C" first="Craig M" last="Williams">Craig M. Williams</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072, Australia.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072</wicri:regionArea></affiliation></author><author><name sortKey="Crassous, Jeanne" sort="Crassous, Jeanne" uniqKey="Crassous J" first="Jeanne" last="Crassous">Jeanne Crassous</name><affiliation wicri:level="1"><nlm:affiliation>Université de Rennes 1, CNRS, UMR 6226, Campus de Beaulieu, 35042, Rennes Cedex, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Université de Rennes 1, CNRS, UMR 6226, Campus de Beaulieu, 35042, Rennes Cedex</wicri:regionArea></affiliation></author><author><name sortKey="Polavarapu, Prasad L" sort="Polavarapu, Prasad L" uniqKey="Polavarapu P" first="Prasad L" last="Polavarapu">Prasad L. Polavarapu</name><affiliation wicri:level="1"><nlm:affiliation>Department of Chemistry, Vanderbilt University, Nashville, TN, 37235, USA.</nlm:affiliation><country xml:lang="fr">États-Unis</country><wicri:regionArea>Department of Chemistry, Vanderbilt University, Nashville, TN, 37235</wicri:regionArea></affiliation></author><author><name sortKey="Crevisy, Christophe" sort="Crevisy, Christophe" uniqKey="Crevisy C" first="Christophe" last="Crévisy">Christophe Crévisy</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author><author><name sortKey="Gerard, Helene" sort="Gerard, Helene" uniqKey="Gerard H" first="Hélène" last="Gérard">Hélène Gérard</name><affiliation wicri:level="1"><nlm:affiliation>Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire de Chimie Théorique CC 137, 4, place Jussieu F., 75252, Paris Cedex 05, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire de Chimie Théorique CC 137, 4, place Jussieu F., 75252, Paris Cedex 05</wicri:regionArea></affiliation></author><author><name sortKey="Mauduit, Marc" sort="Mauduit, Marc" uniqKey="Mauduit M" first="Marc" last="Mauduit">Marc Mauduit</name><affiliation wicri:level="1"><nlm:affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7</wicri:regionArea></affiliation></author></analytic><series><title level="j">Chemistry (Weinheim an der Bergstrasse, Germany)</title><idno type="eISSN">1521-3765</idno><imprint><date when="2017" type="published">2017</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The first stereocontrolled Cu-catalyzed sequential 1,6/1,4-asymmetric conjugate addition (ACA) of C-metalated hard nucleophiles to cyclic dienones is reported. The use of DiPPAM (diphenylphosphinoazomethinylate) followed by a phosphoramidite as the stereoinducing ligands facilitated both high ee values for the 1,6-ACA and high de values for the 1,4-ACA reaction components, which thus gave enantioenriched 1,3-dialkylated moieties. The absolute configurations were determined by using vibrational circular dichroism (VCD) and optical rotatory dispersion (ORD) spectroscopy, in combination with DFT calculations and X-ray analysis. Interestingly, DFT calculations for the mechanism of enantioselective 1,6-addition by using an unprecedented Cu-Zn bimetallic catalytic system confirmed this attribution. Lastly, exploring intramolecular cyclization avenues for enantioenriched 1,3-dialkylated products provided access to the challenging drimane skeleton.</div></front></TEI><pubmed><MedlineCitation Status="In-Data-Review" Owner="NLM"><PMID Version="1">28370488</PMID><DateCreated><Year>2017</Year><Month>04</Month><Day>03</Day></DateCreated><DateRevised><Year>2017</Year><Month>06</Month><Day>01</Day></DateRevised><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Electronic">1521-3765</ISSN><JournalIssue CitedMedium="Internet"><Volume>23</Volume><Issue>31</Issue><PubDate><Year>2017</Year><Month>Jun</Month><Day>01</Day></PubDate></JournalIssue><Title>Chemistry (Weinheim an der Bergstrasse, Germany)</Title><ISOAbbreviation>Chemistry</ISOAbbreviation></Journal><ArticleTitle>Asymmetric Sequential Cu-Catalyzed 1,6/1,4-Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity.</ArticleTitle><Pagination><MedlinePgn>7515-7525</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1002/chem.201606034</ELocationID><Abstract><AbstractText>The first stereocontrolled Cu-catalyzed sequential 1,6/1,4-asymmetric conjugate addition (ACA) of C-metalated hard nucleophiles to cyclic dienones is reported. The use of DiPPAM (diphenylphosphinoazomethinylate) followed by a phosphoramidite as the stereoinducing ligands facilitated both high ee values for the 1,6-ACA and high de values for the 1,4-ACA reaction components, which thus gave enantioenriched 1,3-dialkylated moieties. The absolute configurations were determined by using vibrational circular dichroism (VCD) and optical rotatory dispersion (ORD) spectroscopy, in combination with DFT calculations and X-ray analysis. Interestingly, DFT calculations for the mechanism of enantioselective 1,6-addition by using an unprecedented Cu-Zn bimetallic catalytic system confirmed this attribution. Lastly, exploring intramolecular cyclization avenues for enantioenriched 1,3-dialkylated products provided access to the challenging drimane skeleton.</AbstractText><CopyrightInformation>© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</CopyrightInformation></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Blons</LastName><ForeName>Charlie</ForeName><Initials>C</Initials><AffiliationInfo><Affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Morin</LastName><ForeName>Marie S T</ForeName><Initials>MST</Initials><AffiliationInfo><Affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Schmid</LastName><ForeName>Thibault E</ForeName><Initials>TE</Initials><AffiliationInfo><Affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Vives</LastName><ForeName>Thomas</ForeName><Initials>T</Initials><AffiliationInfo><Affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Colombel-Rouen</LastName><ForeName>Sophie</ForeName><Initials>S</Initials><AffiliationInfo><Affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Baslé</LastName><ForeName>Olivier</ForeName><Initials>O</Initials><Identifier Source="ORCID">http://orcid.org/0000-0002-4551-473X</Identifier><AffiliationInfo><Affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Reynaldo</LastName><ForeName>Thibault</ForeName><Initials>T</Initials><AffiliationInfo><Affiliation>Université de Rennes 1, CNRS, UMR 6226, Campus de Beaulieu, 35042, Rennes Cedex, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Covington</LastName><ForeName>Cody L</ForeName><Initials>CL</Initials><AffiliationInfo><Affiliation>Department of Chemistry, Vanderbilt University, Nashville, TN, 37235, USA.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Halbert</LastName><ForeName>Stéphanie</ForeName><Initials>S</Initials><AffiliationInfo><Affiliation>Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire de Chimie Théorique CC 137, 4, place Jussieu F., 75252, Paris Cedex 05, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Cuskelly</LastName><ForeName>Sean N</ForeName><Initials>SN</Initials><AffiliationInfo><Affiliation>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072, Australia.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Bernhardt</LastName><ForeName>Paul V</ForeName><Initials>PV</Initials><AffiliationInfo><Affiliation>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072, Australia.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Williams</LastName><ForeName>Craig M</ForeName><Initials>CM</Initials><Identifier Source="ORCID">http://orcid.org/0000-0002-3834-7398</Identifier><AffiliationInfo><Affiliation>School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD 4072, Australia.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Crassous</LastName><ForeName>Jeanne</ForeName><Initials>J</Initials><Identifier Source="ORCID">http://orcid.org/0000-0002-4037-6067</Identifier><AffiliationInfo><Affiliation>Université de Rennes 1, CNRS, UMR 6226, Campus de Beaulieu, 35042, Rennes Cedex, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Polavarapu</LastName><ForeName>Prasad L</ForeName><Initials>PL</Initials><Identifier Source="ORCID">http://orcid.org/0000-0001-6458-0508</Identifier><AffiliationInfo><Affiliation>Department of Chemistry, Vanderbilt University, Nashville, TN, 37235, USA.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Crévisy</LastName><ForeName>Christophe</ForeName><Initials>C</Initials><AffiliationInfo><Affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Gérard</LastName><ForeName>Hélène</ForeName><Initials>H</Initials><AffiliationInfo><Affiliation>Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire de Chimie Théorique CC 137, 4, place Jussieu F., 75252, Paris Cedex 05, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Mauduit</LastName><ForeName>Marc</ForeName><Initials>M</Initials><Identifier Source="ORCID">http://orcid.org/0000-0002-7080-9708</Identifier><AffiliationInfo><Affiliation>Ecole Nationale Supérieure de Chimie de Rennes, CNRS UMR 6226, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.</Affiliation></AffiliationInfo></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType UI="D016428">Journal Article</PublicationType></PublicationTypeList><ArticleDate DateType="Electronic"><Year>2017</Year><Month>05</Month><Day>16</Day></ArticleDate></Article><MedlineJournalInfo><Country>Germany</Country><MedlineTA>Chemistry</MedlineTA><NlmUniqueID>9513783</NlmUniqueID><ISSNLinking>0947-6539</ISSNLinking></MedlineJournalInfo><KeywordList Owner="NOTNLM"><Keyword MajorTopicYN="N">asymmetric catalysis</Keyword><Keyword MajorTopicYN="N">circular dichroism</Keyword><Keyword MajorTopicYN="N">configuration determination</Keyword><Keyword MajorTopicYN="N">conjugate addition</Keyword><Keyword MajorTopicYN="N">copper</Keyword></KeywordList></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="received"><Year>2016</Year><Month>12</Month><Day>27</Day></PubMedPubDate><PubMedPubDate PubStatus="revised"><Year>2017</Year><Month>03</Month><Day>08</Day></PubMedPubDate><PubMedPubDate PubStatus="pubmed"><Year>2017</Year><Month>4</Month><Day>4</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2017</Year><Month>4</Month><Day>4</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2017</Year><Month>4</Month><Day>4</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="pubmed">28370488</ArticleId><ArticleId IdType="doi">10.1002/chem.201606034</ArticleId></ArticleIdList></PubmedData></pubmed></record>Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Wicri/Asie/explor/AustralieFrV1/Data/PubMed/Curation
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 000B43 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/PubMed/Curation/biblio.hfd -nk 000B43 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien
|wiki= Wicri/Asie
|area= AustralieFrV1
|flux= PubMed
|étape= Curation
|type= RBID
|clé= pubmed:28370488
|texte= Asymmetric Sequential Cu-Catalyzed 1,6/1,4-Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity.
}}
Pour générer des pages wiki
HfdIndexSelect -h $EXPLOR_AREA/Data/PubMed/Curation/RBID.i -Sk "pubmed:28370488" \
| HfdSelect -Kh $EXPLOR_AREA/Data/PubMed/Curation/biblio.hfd \
| NlmPubMed2Wicri -a AustralieFrV1
| This area was generated with Dilib version V0.6.33. |  |