The mechanism of N-vinylindole formation via tandem imine formation and cycloisomerisation of o-ethynylanilines
Identifieur interne : 007C85 ( Main/Exploration ); précédent : 007C84; suivant : 007C86The mechanism of N-vinylindole formation via tandem imine formation and cycloisomerisation of o-ethynylanilines
Auteurs : Danielle F. Kennedy [Australie] ; Ainara Nova [France] ; Anthony C. Willis [Australie] ; Odile Eisenstein [France] ; Barbara A. Messerle [Australie]Source :
- Dalton Transactions [ 1477-9226 ] ; 2009.
English descriptors
- KwdEn :
- Acetone, Alkyne, Amine, Amine cyclisation, Aniline, Catalysed, Catalyst, Catalytic cycle, Chem, Computational studies, Cpircl2, Cyclisation, Cyclisation step, Dalton trans, Energy barrier, Experimental data, Hydroamination, Hydroamination reaction, Imine, Imine cyclisation, Imine formation, Indole, Indoles, Intramolecular, Intramolecular proton transfer, Kcal, Lett, Metal centre, Mmol, Molar, Molar equivalent, Molar equivalents, Nabf4, Nucleophilic addition, Pathway, Phys, Proton, Proton transfer, Reactant, Reactive form, Royal society, Stationary points, Trans, Transition state, Transition states, Vinyl indole.
- Teeft :
- Acetone, Alkyne, Amine, Amine cyclisation, Aniline, Catalysed, Catalyst, Catalytic cycle, Chem, Computational studies, Cpircl2, Cyclisation, Cyclisation step, Dalton trans, Energy barrier, Experimental data, Hydroamination, Hydroamination reaction, Imine, Imine cyclisation, Imine formation, Indole, Indoles, Intramolecular, Intramolecular proton transfer, Kcal, Lett, Metal centre, Mmol, Molar, Molar equivalent, Molar equivalents, Nabf4, Nucleophilic addition, Pathway, Phys, Proton, Proton transfer, Reactant, Reactive form, Royal society, Stationary points, Trans, Transition state, Transition states, Vinyl indole.
Abstract
The reaction of 2-(2-phenylethynyl)aniline with acetone in presence of [IrCp*Cl2]2 has previously been found to yield a vinyl indole derivative and not the indole expected to form following a hydroamination reaction. Experimental data, including labelling studies, isolation and solid state structure determination of a reaction intermediate together with DFT calculations were used to develop a mechanism for the formation of the vinyl indole. In the mechanism proposed, acetone plays a significant role in several steps of the reaction path, participating in the fragmentation of the dinuclear Ir complex and the formation of the reactive form of the catalyst as well as blocking the formation of the expected hydroamination product by coordination to the Ir catalyst. Coordinated acetone reacts with the aniline to form an imine derivative, which yields the final product following proton transfer promoted by acetone. The proposed mechanism is in good agreement with the experimental data.
Url:
DOI: 10.1039/b915269e
Affiliations:
Links toward previous steps (curation, corpus...)
- to stream Istex, to step Corpus: 001E84
- to stream Istex, to step Curation: 001E84
- to stream Istex, to step Checkpoint: 000C99
- to stream Main, to step Merge: 008377
- to stream Main, to step Curation: 007C85
Le document en format XML
<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title>The mechanism of N-vinylindole formation via tandem imine formation and cycloisomerisation of o-ethynylanilines</title><author wicri:is="90%"><name sortKey="Kennedy, Danielle F" sort="Kennedy, Danielle F" uniqKey="Kennedy D" first="Danielle F." last="Kennedy">Danielle F. Kennedy</name></author><author wicri:is="90%"><name sortKey="Nova, Ainara" sort="Nova, Ainara" uniqKey="Nova A" first="Ainara" last="Nova">Ainara Nova</name></author><author wicri:is="90%"><name sortKey="Willis, Anthony C" sort="Willis, Anthony C" uniqKey="Willis A" first="Anthony C." last="Willis">Anthony C. Willis</name></author><author wicri:is="90%"><name sortKey="Eisenstein, Odile" sort="Eisenstein, Odile" uniqKey="Eisenstein O" first="Odile" last="Eisenstein">Odile Eisenstein</name></author><author wicri:is="90%"><name sortKey="Messerle, Barbara A" sort="Messerle, Barbara A" uniqKey="Messerle B" first="Barbara A." last="Messerle">Barbara A. Messerle</name></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:A2E6E110AB7CF3D90AC1BDD98309998923962CB6</idno><date when="2009" year="2009">2009</date><idno type="doi">10.1039/b915269e</idno><idno type="url">https://api.istex.fr/document/A2E6E110AB7CF3D90AC1BDD98309998923962CB6/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">001E84</idno><idno type="wicri:explorRef" wicri:stream="Istex" wicri:step="Corpus" wicri:corpus="ISTEX">001E84</idno><idno type="wicri:Area/Istex/Curation">001E84</idno><idno type="wicri:Area/Istex/Checkpoint">000C99</idno><idno type="wicri:explorRef" wicri:stream="Istex" wicri:step="Checkpoint">000C99</idno><idno type="wicri:doubleKey">1477-9226:2009:Kennedy D:the:mechanism:of</idno><idno type="wicri:Area/Main/Merge">008377</idno><idno type="wicri:Area/Main/Curation">007C85</idno><idno type="wicri:Area/Main/Exploration">007C85</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a">The mechanism of N-vinylindole formation via tandem imine formation and cycloisomerisation of o-ethynylanilines</title><author wicri:is="90%"><name sortKey="Kennedy, Danielle F" sort="Kennedy, Danielle F" uniqKey="Kennedy D" first="Danielle F." last="Kennedy">Danielle F. Kennedy</name><affiliation wicri:level="3"><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry, The University of New South Wales, 2052, N.S.W., Sydney</wicri:regionArea><placeName><settlement type="city">Sydney</settlement><region type="état">Nouvelle-Galles du Sud</region></placeName></affiliation><affiliation wicri:level="1"><country wicri:rule="url">Australie</country></affiliation></author><author wicri:is="90%"><name sortKey="Nova, Ainara" sort="Nova, Ainara" uniqKey="Nova A" first="Ainara" last="Nova">Ainara Nova</name><affiliation wicri:level="1"><country xml:lang="fr">France</country><wicri:regionArea>Institut Charles Gerhardt, Universit Montpellier 2, 34095, CNRS 5253, cc 1501, Place Eugne Bataillon, Montpellier Cedex 5</wicri:regionArea><wicri:noRegion>Montpellier Cedex 5</wicri:noRegion><wicri:noRegion>Montpellier Cedex 5</wicri:noRegion></affiliation><affiliation wicri:level="1"><country wicri:rule="url">France</country></affiliation></author><author wicri:is="90%"><name sortKey="Willis, Anthony C" sort="Willis, Anthony C" uniqKey="Willis A" first="Anthony C." last="Willis">Anthony C. Willis</name><affiliation wicri:level="1"><country xml:lang="fr">Australie</country><wicri:regionArea>Research School of Chemistry, The Australian National University, 0200, A.C.T., Canberra</wicri:regionArea><wicri:noRegion>Canberra</wicri:noRegion></affiliation></author><author wicri:is="90%"><name sortKey="Eisenstein, Odile" sort="Eisenstein, Odile" uniqKey="Eisenstein O" first="Odile" last="Eisenstein">Odile Eisenstein</name><affiliation wicri:level="1"><country xml:lang="fr">France</country><wicri:regionArea>Institut Charles Gerhardt, Universit Montpellier 2, 34095, CNRS 5253, cc 1501, Place Eugne Bataillon, Montpellier Cedex 5</wicri:regionArea><wicri:noRegion>Montpellier Cedex 5</wicri:noRegion><wicri:noRegion>Montpellier Cedex 5</wicri:noRegion></affiliation><affiliation wicri:level="1"><country wicri:rule="url">France</country></affiliation></author><author wicri:is="90%"><name sortKey="Messerle, Barbara A" sort="Messerle, Barbara A" uniqKey="Messerle B" first="Barbara A." last="Messerle">Barbara A. Messerle</name><affiliation wicri:level="3"><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry, The University of New South Wales, 2052, N.S.W., Sydney</wicri:regionArea><placeName><settlement type="city">Sydney</settlement><region type="état">Nouvelle-Galles du Sud</region></placeName></affiliation><affiliation wicri:level="1"><country wicri:rule="url">Australie</country></affiliation></author></analytic><monogr></monogr><series><title level="j">Dalton Transactions</title><title level="j" type="abbrev">Dalton Trans.</title><idno type="ISSN">1477-9226</idno><idno type="eISSN">1477-9234</idno><imprint><publisher>The Royal Society of Chemistry.</publisher><date type="published" when="2009">2009</date><biblScope unit="volume"></biblScope><biblScope unit="issue">46</biblScope><biblScope unit="page" from="10296">10296</biblScope><biblScope unit="page" to="10304">10304</biblScope></imprint><idno type="ISSN">1477-9226</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">1477-9226</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Acetone</term><term>Alkyne</term><term>Amine</term><term>Amine cyclisation</term><term>Aniline</term><term>Catalysed</term><term>Catalyst</term><term>Catalytic cycle</term><term>Chem</term><term>Computational studies</term><term>Cpircl2</term><term>Cyclisation</term><term>Cyclisation step</term><term>Dalton trans</term><term>Energy barrier</term><term>Experimental data</term><term>Hydroamination</term><term>Hydroamination reaction</term><term>Imine</term><term>Imine cyclisation</term><term>Imine formation</term><term>Indole</term><term>Indoles</term><term>Intramolecular</term><term>Intramolecular proton transfer</term><term>Kcal</term><term>Lett</term><term>Metal centre</term><term>Mmol</term><term>Molar</term><term>Molar equivalent</term><term>Molar equivalents</term><term>Nabf4</term><term>Nucleophilic addition</term><term>Pathway</term><term>Phys</term><term>Proton</term><term>Proton transfer</term><term>Reactant</term><term>Reactive form</term><term>Royal society</term><term>Stationary points</term><term>Trans</term><term>Transition state</term><term>Transition states</term><term>Vinyl indole</term></keywords><keywords scheme="Teeft" xml:lang="en"><term>Acetone</term><term>Alkyne</term><term>Amine</term><term>Amine cyclisation</term><term>Aniline</term><term>Catalysed</term><term>Catalyst</term><term>Catalytic cycle</term><term>Chem</term><term>Computational studies</term><term>Cpircl2</term><term>Cyclisation</term><term>Cyclisation step</term><term>Dalton trans</term><term>Energy barrier</term><term>Experimental data</term><term>Hydroamination</term><term>Hydroamination reaction</term><term>Imine</term><term>Imine cyclisation</term><term>Imine formation</term><term>Indole</term><term>Indoles</term><term>Intramolecular</term><term>Intramolecular proton transfer</term><term>Kcal</term><term>Lett</term><term>Metal centre</term><term>Mmol</term><term>Molar</term><term>Molar equivalent</term><term>Molar equivalents</term><term>Nabf4</term><term>Nucleophilic addition</term><term>Pathway</term><term>Phys</term><term>Proton</term><term>Proton transfer</term><term>Reactant</term><term>Reactive form</term><term>Royal society</term><term>Stationary points</term><term>Trans</term><term>Transition state</term><term>Transition states</term><term>Vinyl indole</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract">The reaction of 2-(2-phenylethynyl)aniline with acetone in presence of [IrCp*Cl2]2 has previously been found to yield a vinyl indole derivative and not the indole expected to form following a hydroamination reaction. Experimental data, including labelling studies, isolation and solid state structure determination of a reaction intermediate together with DFT calculations were used to develop a mechanism for the formation of the vinyl indole. In the mechanism proposed, acetone plays a significant role in several steps of the reaction path, participating in the fragmentation of the dinuclear Ir complex and the formation of the reactive form of the catalyst as well as blocking the formation of the expected hydroamination product by coordination to the Ir catalyst. Coordinated acetone reacts with the aniline to form an imine derivative, which yields the final product following proton transfer promoted by acetone. The proposed mechanism is in good agreement with the experimental data.</div></front></TEI><affiliations><list><country><li>Australie</li><li>France</li></country><region><li>Nouvelle-Galles du Sud</li></region><settlement><li>Sydney</li></settlement></list><tree><country name="Australie"><region name="Nouvelle-Galles du Sud"><name sortKey="Kennedy, Danielle F" sort="Kennedy, Danielle F" uniqKey="Kennedy D" first="Danielle F." last="Kennedy">Danielle F. Kennedy</name></region><name sortKey="Kennedy, Danielle F" sort="Kennedy, Danielle F" uniqKey="Kennedy D" first="Danielle F." last="Kennedy">Danielle F. Kennedy</name><name sortKey="Messerle, Barbara A" sort="Messerle, Barbara A" uniqKey="Messerle B" first="Barbara A." last="Messerle">Barbara A. Messerle</name><name sortKey="Messerle, Barbara A" sort="Messerle, Barbara A" uniqKey="Messerle B" first="Barbara A." last="Messerle">Barbara A. Messerle</name><name sortKey="Willis, Anthony C" sort="Willis, Anthony C" uniqKey="Willis A" first="Anthony C." last="Willis">Anthony C. Willis</name></country><country name="France"><noRegion><name sortKey="Nova, Ainara" sort="Nova, Ainara" uniqKey="Nova A" first="Ainara" last="Nova">Ainara Nova</name></noRegion><name sortKey="Eisenstein, Odile" sort="Eisenstein, Odile" uniqKey="Eisenstein O" first="Odile" last="Eisenstein">Odile Eisenstein</name><name sortKey="Eisenstein, Odile" sort="Eisenstein, Odile" uniqKey="Eisenstein O" first="Odile" last="Eisenstein">Odile Eisenstein</name><name sortKey="Nova, Ainara" sort="Nova, Ainara" uniqKey="Nova A" first="Ainara" last="Nova">Ainara Nova</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Wicri/Asie/explor/AustralieFrV1/Data/Main/Exploration
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 007C85 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/Main/Exploration/biblio.hfd -nk 007C85 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien
|wiki= Wicri/Asie
|area= AustralieFrV1
|flux= Main
|étape= Exploration
|type= RBID
|clé= ISTEX:A2E6E110AB7CF3D90AC1BDD98309998923962CB6
|texte= The mechanism of N-vinylindole formation via tandem imine formation and cycloisomerisation of o-ethynylanilines
}}
| This area was generated with Dilib version V0.6.33. |  |