Adding a Structural Context to the Deprotometalation and Trans-Metal Trapping Chemistry of Phenyl-Substituted Benzotriazole.
Identifieur interne : 000387 ( PubMed/Corpus ); précédent : 000386; suivant : 000388Adding a Structural Context to the Deprotometalation and Trans-Metal Trapping Chemistry of Phenyl-Substituted Benzotriazole.
Auteurs : M Ngeles Fuentes ; Alan R. Kennedy ; Robert E. Mulvey ; John A. Parkinson ; Toni Rantanen ; Stuart D. Robertson ; Victor SnieckusSource :
- Chemistry (Weinheim an der Bergstrasse, Germany) [ 1521-3765 ] ; 2015.
Abstract
Organometallic bases are becoming increasingly complex, because mixing components can lead to bases superior to single-component bases. To better understand this superiority, it is useful to study metalated intermediate structures prior to quenching. This study is on 1-phenyl-1H-benzotriazole, which was previously deprotonated by an in situ ZnCl2 ⋅TMEDA/LiTMP (TMEDA=N,N,N',N'-tetramethylethylenediamine; TMP=2,2,6,6-tetramethylpiperidide) mixture and then iodinated. Herein, reaction with LiTMP exposes the deficiency of the single-component base as the crystalline product obtained was [{4-R-1-(2-lithiophenyl)-1H-benzotriazole⋅3THF}2 ], [R=2-C6 H4 (Ph)NLi], in which ring opening of benzotriazole and N2 extrusion had occurred. Supporting lithiation by adding iBu2 Al(TMP) induces trans-metal trapping, in which C-Li bonds transform into C-Al bonds to stabilise the metalated intermediate. X-ray diffraction studies revealed homodimeric [(4-R'-1-phenyl-1H-benzotriazole)2 ], [R'=(iBu)2 Al(μ-TMP)Li], and its heterodimeric isomer [(4-R'-1-phenyl-1H-benzotriazole){2-R'-1-phenyl-1H-benzotriazole}], whose structure and slow conformational dynamics were probed by solution NMR spectroscopy.
DOI: 10.1002/chem.201502534
PubMed: 26387678
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Mulvey</name><affiliation><nlm:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44) 141-548-4787. r.e.mulvey@strath.ac.uk.</nlm:affiliation></affiliation></author><author><name sortKey="Parkinson, John A" sort="Parkinson, John A" uniqKey="Parkinson J" first="John A" last="Parkinson">John A. Parkinson</name><affiliation><nlm:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44) 141-548-4787.</nlm:affiliation></affiliation></author><author><name sortKey="Rantanen, Toni" sort="Rantanen, Toni" uniqKey="Rantanen T" first="Toni" last="Rantanen">Toni Rantanen</name><affiliation><nlm:affiliation>Snieckus Innovations, Innovation Park, 945 Princess Street, Kingston, Ontario, K7L 3N6 (Canada).</nlm:affiliation></affiliation></author><author><name sortKey="Robertson, Stuart D" sort="Robertson, Stuart D" uniqKey="Robertson S" first="Stuart D" last="Robertson">Stuart D. Robertson</name><affiliation><nlm:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44) 141-548-4787.</nlm:affiliation></affiliation></author><author><name sortKey="Snieckus, Victor" sort="Snieckus, Victor" uniqKey="Snieckus V" first="Victor" last="Snieckus">Victor Snieckus</name><affiliation><nlm:affiliation>Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario, K7L 3N6 (Canada).</nlm:affiliation></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">PubMed</idno><date when="2015">2015</date><idno type="RBID">pubmed:26387678</idno><idno type="pmid">26387678</idno><idno type="doi">10.1002/chem.201502534</idno><idno type="wicri:Area/PubMed/Corpus">000387</idno><idno type="wicri:explorRef" wicri:stream="PubMed" wicri:step="Corpus" wicri:corpus="PubMed">000387</idno></publicationStmt><sourceDesc><biblStruct><analytic><title xml:lang="en">Adding a Structural Context to the Deprotometalation and Trans-Metal Trapping Chemistry of Phenyl-Substituted Benzotriazole.</title><author><name sortKey="Fuentes, M Ngeles" sort="Fuentes, M Ngeles" uniqKey="Fuentes M" first="M Ngeles" last="Fuentes">M Ngeles Fuentes</name><affiliation><nlm:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44) 141-548-4787.</nlm:affiliation></affiliation></author><author><name sortKey="Kennedy, Alan R" sort="Kennedy, Alan R" uniqKey="Kennedy A" first="Alan R" last="Kennedy">Alan R. Kennedy</name><affiliation><nlm:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44) 141-548-4787.</nlm:affiliation></affiliation></author><author><name sortKey="Mulvey, Robert E" sort="Mulvey, Robert E" uniqKey="Mulvey R" first="Robert E" last="Mulvey">Robert E. Mulvey</name><affiliation><nlm:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44) 141-548-4787. r.e.mulvey@strath.ac.uk.</nlm:affiliation></affiliation></author><author><name sortKey="Parkinson, John A" sort="Parkinson, John A" uniqKey="Parkinson J" first="John A" last="Parkinson">John A. Parkinson</name><affiliation><nlm:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44) 141-548-4787.</nlm:affiliation></affiliation></author><author><name sortKey="Rantanen, Toni" sort="Rantanen, Toni" uniqKey="Rantanen T" first="Toni" last="Rantanen">Toni Rantanen</name><affiliation><nlm:affiliation>Snieckus Innovations, Innovation Park, 945 Princess Street, Kingston, Ontario, K7L 3N6 (Canada).</nlm:affiliation></affiliation></author><author><name sortKey="Robertson, Stuart D" sort="Robertson, Stuart D" uniqKey="Robertson S" first="Stuart D" last="Robertson">Stuart D. Robertson</name><affiliation><nlm:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44) 141-548-4787.</nlm:affiliation></affiliation></author><author><name sortKey="Snieckus, Victor" sort="Snieckus, Victor" uniqKey="Snieckus V" first="Victor" last="Snieckus">Victor Snieckus</name><affiliation><nlm:affiliation>Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario, K7L 3N6 (Canada).</nlm:affiliation></affiliation></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></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Organometallic bases are becoming increasingly complex, because mixing components can lead to bases superior to single-component bases. To better understand this superiority, it is useful to study metalated intermediate structures prior to quenching. This study is on 1-phenyl-1H-benzotriazole, which was previously deprotonated by an in situ ZnCl2 ⋅TMEDA/LiTMP (TMEDA=N,N,N',N'-tetramethylethylenediamine; TMP=2,2,6,6-tetramethylpiperidide) mixture and then iodinated. Herein, reaction with LiTMP exposes the deficiency of the single-component base as the crystalline product obtained was [{4-R-1-(2-lithiophenyl)-1H-benzotriazole⋅3THF}2 ], [R=2-C6 H4 (Ph)NLi], in which ring opening of benzotriazole and N2 extrusion had occurred. Supporting lithiation by adding iBu2 Al(TMP) induces trans-metal trapping, in which C-Li bonds transform into C-Al bonds to stabilise the metalated intermediate. X-ray diffraction studies revealed homodimeric [(4-R'-1-phenyl-1H-benzotriazole)2 ], [R'=(iBu)2 Al(μ-TMP)Li], and its heterodimeric isomer [(4-R'-1-phenyl-1H-benzotriazole){2-R'-1-phenyl-1H-benzotriazole}], whose structure and slow conformational dynamics were probed by solution NMR spectroscopy.</div></front></TEI><pubmed><MedlineCitation Status="PubMed-not-MEDLINE" Owner="NLM"><PMID Version="1">26387678</PMID><DateCreated><Year>2015</Year><Month>10</Month><Day>03</Day></DateCreated><DateCompleted><Year>2015</Year><Month>12</Month><Day>30</Day></DateCompleted><DateRevised><Year>2015</Year><Month>10</Month><Day>03</Day></DateRevised><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Electronic">1521-3765</ISSN><JournalIssue CitedMedium="Internet"><Volume>21</Volume><Issue>42</Issue><PubDate><Year>2015</Year><Month>Oct</Month><Day>12</Day></PubDate></JournalIssue><Title>Chemistry (Weinheim an der Bergstrasse, Germany)</Title><ISOAbbreviation>Chemistry</ISOAbbreviation></Journal><ArticleTitle>Adding a Structural Context to the Deprotometalation and Trans-Metal Trapping Chemistry of Phenyl-Substituted Benzotriazole.</ArticleTitle><Pagination><MedlinePgn>14812-22</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1002/chem.201502534</ELocationID><Abstract><AbstractText>Organometallic bases are becoming increasingly complex, because mixing components can lead to bases superior to single-component bases. To better understand this superiority, it is useful to study metalated intermediate structures prior to quenching. This study is on 1-phenyl-1H-benzotriazole, which was previously deprotonated by an in situ ZnCl2 ⋅TMEDA/LiTMP (TMEDA=N,N,N',N'-tetramethylethylenediamine; TMP=2,2,6,6-tetramethylpiperidide) mixture and then iodinated. Herein, reaction with LiTMP exposes the deficiency of the single-component base as the crystalline product obtained was [{4-R-1-(2-lithiophenyl)-1H-benzotriazole⋅3THF}2 ], [R=2-C6 H4 (Ph)NLi], in which ring opening of benzotriazole and N2 extrusion had occurred. Supporting lithiation by adding iBu2 Al(TMP) induces trans-metal trapping, in which C-Li bonds transform into C-Al bonds to stabilise the metalated intermediate. X-ray diffraction studies revealed homodimeric [(4-R'-1-phenyl-1H-benzotriazole)2 ], [R'=(iBu)2 Al(μ-TMP)Li], and its heterodimeric isomer [(4-R'-1-phenyl-1H-benzotriazole){2-R'-1-phenyl-1H-benzotriazole}], whose structure and slow conformational dynamics were probed by solution NMR spectroscopy.</AbstractText><CopyrightInformation>© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</CopyrightInformation></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Fuentes</LastName><ForeName>M Ángeles</ForeName><Initials>MÁ</Initials><AffiliationInfo><Affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44) 141-548-4787.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Kennedy</LastName><ForeName>Alan R</ForeName><Initials>AR</Initials><AffiliationInfo><Affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44) 141-548-4787.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Mulvey</LastName><ForeName>Robert E</ForeName><Initials>RE</Initials><AffiliationInfo><Affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44) 141-548-4787. r.e.mulvey@strath.ac.uk.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Parkinson</LastName><ForeName>John A</ForeName><Initials>JA</Initials><AffiliationInfo><Affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44) 141-548-4787.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Rantanen</LastName><ForeName>Toni</ForeName><Initials>T</Initials><AffiliationInfo><Affiliation>Snieckus Innovations, Innovation Park, 945 Princess Street, Kingston, Ontario, K7L 3N6 (Canada).</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Robertson</LastName><ForeName>Stuart D</ForeName><Initials>SD</Initials><AffiliationInfo><Affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44) 141-548-4787.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Snieckus</LastName><ForeName>Victor</ForeName><Initials>V</Initials><AffiliationInfo><Affiliation>Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario, K7L 3N6 (Canada).</Affiliation></AffiliationInfo></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType UI="D016428">Journal Article</PublicationType></PublicationTypeList><ArticleDate DateType="Electronic"><Year>2015</Year><Month>09</Month><Day>21</Day></ArticleDate></Article><MedlineJournalInfo><Country>Germany</Country><MedlineTA>Chemistry</MedlineTA><NlmUniqueID>9513783</NlmUniqueID><ISSNLinking>0947-6539</ISSNLinking></MedlineJournalInfo><KeywordList Owner="NOTNLM"><Keyword MajorTopicYN="N">lithium</Keyword><Keyword MajorTopicYN="N">metalation</Keyword><Keyword MajorTopicYN="N">structure elucidation</Keyword><Keyword MajorTopicYN="N">triazoles</Keyword><Keyword MajorTopicYN="N">zinc</Keyword></KeywordList></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="received"><Year>2015</Year><Month>06</Month><Day>29</Day></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2015</Year><Month>9</Month><Day>22</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="pubmed"><Year>2015</Year><Month>9</Month><Day>22</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2015</Year><Month>9</Month><Day>22</Day><Hour>6</Hour><Minute>1</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="pubmed">26387678</ArticleId><ArticleId IdType="doi">10.1002/chem.201502534</ArticleId></ArticleIdList></PubmedData></pubmed></record>Pour manipuler ce document sous Unix (Dilib)
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