A Practical Transition Metal‐Free Aryl‐Aryl Coupling Method: Arynes as Key Intermediates
Identifieur interne : 001723 ( Istex/Corpus ); précédent : 001722; suivant : 001724A Practical Transition Metal‐Free Aryl‐Aryl Coupling Method: Arynes as Key Intermediates
Auteurs : Frédéric Leroux ; Laurence Bonnafoux ; Christophe Heiss ; Françoise Colobert ; Don Antoine LanfranchiSource :
- Advanced Synthesis & Catalysis [ 1615-4150 ] ; 2007-12-10.
English descriptors
- KwdEn :
- Aqueous solution, Aryllithium, Aryne, Aryne source, Biaryl, Biaryls, Biphenyl, Butyllithium, Catal, Chem, Chlorodicyclohexylphosphine, Colorless, Colorless cubes, Colorless needles, Column chromatography, Cyclohexane, Diethyl, Diethyl ether, Diphosphine ligands, Eluent, Ethanol, Ether, Gmbh, Hexane, Hours period, Kgaa, Leroux, Ligand, Mmol, Organic layers, Practical transition, Reaction mixture, Room temperature, Schlosser, Silica, Sodium sulfate, Sulfate, Synth, Tetrahydrofuran, Trisubstituted biaryls, Update, Updates scheme, Verlag, Verlag gmbh, Weinheim.
- Teeft :
- Aqueous solution, Aryllithium, Aryne, Aryne source, Biaryl, Biaryls, Biphenyl, Butyllithium, Catal, Chem, Chlorodicyclohexylphosphine, Colorless, Colorless cubes, Colorless needles, Column chromatography, Cyclohexane, Diethyl, Diethyl ether, Diphosphine ligands, Eluent, Ethanol, Ether, Gmbh, Hexane, Hours period, Kgaa, Leroux, Ligand, Mmol, Organic layers, Practical transition, Reaction mixture, Room temperature, Schlosser, Silica, Sodium sulfate, Sulfate, Synth, Tetrahydrofuran, Trisubstituted biaryls, Update, Updates scheme, Verlag, Verlag gmbh, Weinheim.
Abstract
Upon treatment of various aryllithium intermediates with 1,2‐dibromobenzene or 1‐bromo‐2‐iodobenzene, dissymmetrical ortho,ortho′‐di‐, tri‐ and even tetrasubstituted bromo‐ or iodobiaryls become readily available. The crucial steps in all these reactions were the nucleophilic addition of the organolithium precursor to a transient aryne species released from it by β‐elimination of a lithium halide and, stabilization of the resulting 2‐biaryllithium intermediate by in situ transfer of bromine or iodine from the starting material. This straightforward transition metal‐free access to biaryls allows the preparation of highly valuable halobiaryls on a gram scale in excellent yields. These precursors can be subsequently functionalized by highly regioselective halogen/metal permutations into a vast variety of target molecules. This was demonstrated in the synthesis of several mono‐ and diphosphine ligands.
Url:
DOI: 10.1002/adsc.200700211
Links to Exploration step
ISTEX:252E46DC67C2FC99E026E4362FC0A53AA2FD6591Le document en format XML
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Frederic" uniqKey="Leroux F" first="Frédéric" last="Leroux">Frédéric Leroux</name><affiliation><mods:affiliation>E-mail: frederic.leroux@ecpm.u‐strasbg.fr</mods:affiliation></affiliation><affiliation><mods:affiliation>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: frederic.leroux@ecpm.u‐strasbg.fr</mods:affiliation></affiliation></author><author><name sortKey="Bonnafoux, Laurence" sort="Bonnafoux, Laurence" uniqKey="Bonnafoux L" first="Laurence" last="Bonnafoux">Laurence Bonnafoux</name><affiliation><mods:affiliation>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742</mods:affiliation></affiliation></author><author><name sortKey="Heiss, Christophe" sort="Heiss, Christophe" uniqKey="Heiss C" first="Christophe" 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scheme="Teeft" xml:lang="en"><term>Aqueous solution</term><term>Aryllithium</term><term>Aryne</term><term>Aryne source</term><term>Biaryl</term><term>Biaryls</term><term>Biphenyl</term><term>Butyllithium</term><term>Catal</term><term>Chem</term><term>Chlorodicyclohexylphosphine</term><term>Colorless</term><term>Colorless cubes</term><term>Colorless needles</term><term>Column chromatography</term><term>Cyclohexane</term><term>Diethyl</term><term>Diethyl ether</term><term>Diphosphine ligands</term><term>Eluent</term><term>Ethanol</term><term>Ether</term><term>Gmbh</term><term>Hexane</term><term>Hours period</term><term>Kgaa</term><term>Leroux</term><term>Ligand</term><term>Mmol</term><term>Organic layers</term><term>Practical transition</term><term>Reaction mixture</term><term>Room temperature</term><term>Schlosser</term><term>Silica</term><term>Sodium sulfate</term><term>Sulfate</term><term>Synth</term><term>Tetrahydrofuran</term><term>Trisubstituted biaryls</term><term>Update</term><term>Updates scheme</term><term>Verlag</term><term>Verlag gmbh</term><term>Weinheim</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Upon treatment of various aryllithium intermediates with 1,2‐dibromobenzene or 1‐bromo‐2‐iodobenzene, dissymmetrical ortho,ortho′‐di‐, tri‐ and even tetrasubstituted bromo‐ or iodobiaryls become readily available. The crucial steps in all these reactions were the nucleophilic addition of the organolithium precursor to a transient aryne species released from it by β‐elimination of a lithium halide and, stabilization of the resulting 2‐biaryllithium intermediate by in situ transfer of bromine or iodine from the starting material. This straightforward transition metal‐free access to biaryls allows the preparation of highly valuable halobiaryls on a gram scale in excellent yields. These precursors can be subsequently functionalized by highly regioselective halogen/metal permutations into a vast variety of target molecules. This was demonstrated in the synthesis of several mono‐ and diphosphine ligands.</div></front></TEI><istex><corpusName>wiley</corpusName><keywords><teeft><json:string>mmol</json:string><json:string>chem</json:string><json:string>tetrahydrofuran</json:string><json:string>biaryls</json:string><json:string>biphenyl</json:string><json:string>butyllithium</json:string><json:string>aryne</json:string><json:string>leroux</json:string><json:string>colorless needles</json:string><json:string>aryllithium</json:string><json:string>diethyl</json:string><json:string>diethyl ether</json:string><json:string>weinheim</json:string><json:string>catal</json:string><json:string>hexane</json:string><json:string>synth</json:string><json:string>verlag</json:string><json:string>kgaa</json:string><json:string>gmbh</json:string><json:string>verlag gmbh</json:string><json:string>schlosser</json:string><json:string>sodium sulfate</json:string><json:string>reaction mixture</json:string><json:string>organic layers</json:string><json:string>sulfate</json:string><json:string>biaryl</json:string><json:string>chlorodicyclohexylphosphine</json:string><json:string>cyclohexane</json:string><json:string>column chromatography</json:string><json:string>eluent</json:string><json:string>ether</json:string><json:string>practical transition</json:string><json:string>ligand</json:string><json:string>update</json:string><json:string>colorless</json:string><json:string>ethanol</json:string><json:string>diphosphine ligands</json:string><json:string>aqueous solution</json:string><json:string>hours period</json:string><json:string>room temperature</json:string><json:string>aryne source</json:string><json:string>trisubstituted biaryls</json:string><json:string>colorless cubes</json:string><json:string>updates scheme</json:string><json:string>silica</json:string></teeft></keywords><author><json:item><name>Frédéric R. Leroux</name><affiliations><json:string>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742</json:string><json:string>E-mail: frederic.leroux@ecpm.u‐strasbg.fr</json:string></affiliations></json:item><json:item><name>Laurence Bonnafoux</name><affiliations><json:string>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742</json:string></affiliations></json:item><json:item><name>Christophe Heiss</name><affiliations><json:string>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742</json:string></affiliations></json:item><json:item><name>Françoise Colobert</name><affiliations><json:string>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742</json:string></affiliations></json:item><json:item><name>Don Antoine Lanfranchi</name><affiliations><json:string>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>arynes</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>biaryls</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>CC coupling</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>halogen/metal exchange</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>phosphines</value></json:item></subject><articleId><json:string>ADSC200700211</json:string></articleId><language><json:string>eng</json:string></language><originalGenre><json:string>miscellaneous</json:string></originalGenre><abstract>Upon treatment of various aryllithium intermediates with 1,2‐dibromobenzene or 1‐bromo‐2‐iodobenzene, dissymmetrical ortho,ortho′‐di‐, tri‐ and even tetrasubstituted bromo‐ or iodobiaryls become readily available. The crucial steps in all these reactions were the nucleophilic addition of the organolithium precursor to a transient aryne species released from it by β‐elimination of a lithium halide and, stabilization of the resulting 2‐biaryllithium intermediate by in situ transfer of bromine or iodine from the starting material. This straightforward transition metal‐free access to biaryls allows the preparation of highly valuable halobiaryls on a gram scale in excellent yields. These precursors can be subsequently functionalized by highly regioselective halogen/metal permutations into a vast variety of target molecules. This was demonstrated in the synthesis of several mono‐ and diphosphine ligands.</abstract><qualityIndicators><score>6.089</score><pdfVersion>1.3</pdfVersion><pdfPageSize>595 x 842 pts (A4)</pdfPageSize><refBibsNative>true</refBibsNative><abstractCharCount>911</abstractCharCount><pdfWordCount>4637</pdfWordCount><pdfCharCount>30427</pdfCharCount><pdfPageCount>9</pdfPageCount><abstractWordCount>121</abstractWordCount></qualityIndicators><title>A Practical Transition Metal‐Free Aryl‐Aryl Coupling Method: Arynes as Key Intermediates</title><genre><json:string>other</json:string></genre><host><title>Advanced Synthesis & Catalysis</title><language><json:string>unknown</json:string></language><doi><json:string>10.1002/(ISSN)1615-4169</json:string></doi><issn><json:string>1615-4150</json:string></issn><eissn><json:string>1615-4169</json:string></eissn><publisherId><json:string>ADSC</json:string></publisherId><volume>349</volume><issue>17‐18</issue><pages><first>2705</first><last>2713</last><total>9</total></pages><genre><json:string>journal</json:string></genre><subject><json:item><value>Update</value></json:item></subject></host><categories><inist><json:string>sciences appliquees, technologies et medecines</json:string><json:string>sciences biologiques et medicales</json:string><json:string>sciences biologiques fondamentales et appliquees. psychologie</json:string><json:string>phytopathologie. zoologie agricole. protection des cultures et des forets</json:string></inist></categories><publicationDate>2007</publicationDate><copyrightDate>2007</copyrightDate><doi><json:string>10.1002/adsc.200700211</json:string></doi><id>252E46DC67C2FC99E026E4362FC0A53AA2FD6591</id><score>1</score><fulltext><json:item><extension>pdf</extension><original>true</original><mimetype>application/pdf</mimetype><uri>https://api.istex.fr/document/252E46DC67C2FC99E026E4362FC0A53AA2FD6591/fulltext/pdf</uri></json:item><json:item><extension>zip</extension><original>false</original><mimetype>application/zip</mimetype><uri>https://api.istex.fr/document/252E46DC67C2FC99E026E4362FC0A53AA2FD6591/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/252E46DC67C2FC99E026E4362FC0A53AA2FD6591/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a" type="main" xml:lang="en">A Practical Transition Metal‐Free Aryl‐Aryl Coupling Method: Arynes as Key Intermediates</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><availability><licence>Copyright © 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</licence></availability><date type="published" when="2007-12-10"></date></publicationStmt><notesStmt><note type="content-type" subtype="other" source="miscellaneous" scheme="https://content-type.data.istex.fr/ark:/67375/XTP-7474895G-0">other</note><note type="publication-type" subtype="journal" scheme="https://publication-type.data.istex.fr/ark:/67375/JMC-0GLKJH51-B">journal</note></notesStmt><sourceDesc><biblStruct type="other"><analytic><title level="a" type="main" xml:lang="en">A Practical Transition Metal‐Free Aryl‐Aryl Coupling Method: Arynes as Key Intermediates</title><author xml:id="author-0000"><persName><forename type="first">Frédéric R.</forename><surname>Leroux</surname></persName><email>frederic.leroux@ecpm.u‐strasbg.fr</email><affiliation>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742<address><country key="FR"></country></address></affiliation></author><author xml:id="author-0001"><persName><forename type="first">Laurence</forename><surname>Bonnafoux</surname></persName><affiliation>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742<address><country key="FR"></country></address></affiliation></author><author xml:id="author-0002"><persName><forename type="first">Christophe</forename><surname>Heiss</surname></persName><affiliation>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742<address><country key="FR"></country></address></affiliation></author><author xml:id="author-0003"><persName><forename type="first">Françoise</forename><surname>Colobert</surname></persName><affiliation>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742<address><country key="FR"></country></address></affiliation></author><author xml:id="author-0004"><persName><forename type="first">Don Antoine</forename><surname>Lanfranchi</surname></persName><affiliation>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742<address><country key="FR"></country></address></affiliation></author><idno type="istex">252E46DC67C2FC99E026E4362FC0A53AA2FD6591</idno><idno type="ark">ark:/67375/WNG-KCK6PWF1-N</idno><idno type="DOI">10.1002/adsc.200700211</idno><idno type="unit">ADSC200700211</idno><idno type="toTypesetVersion">file:ADSC.ADSC200700211.pdf</idno></analytic><monogr><title level="j" type="main">Advanced Synthesis & Catalysis</title><title level="j" type="sub">Dedicated Cluster</title><title level="j" type="alt">ADVANCED SYNTHESIS CATALYSIS</title><idno type="pISSN">1615-4150</idno><idno type="eISSN">1615-4169</idno><idno type="book-DOI">10.1002/(ISSN)1615-4169</idno><idno type="book-part-DOI">10.1002/adsc.v349:17/18</idno><idno type="product">ADSC</idno><imprint><biblScope unit="vol">349</biblScope><biblScope unit="issue">17‐18</biblScope><biblScope unit="page" from="2705">2705</biblScope><biblScope unit="page" to="2713">2713</biblScope><biblScope unit="page-count">9</biblScope><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2007-12-10"></date></imprint></monogr></biblStruct></sourceDesc></fileDesc><profileDesc><abstract xml:lang="en" style="main"><head>Abstract</head><p>Upon treatment of various aryllithium intermediates with 1,2‐dibromobenzene or 1‐bromo‐2‐iodobenzene, dissymmetrical <hi rend="italic">ortho,ortho′</hi>‐di‐, tri‐ and even tetrasubstituted bromo‐ or iodobiaryls become readily available. The crucial steps in all these reactions were the nucleophilic addition of the organolithium precursor to a transient aryne species released from it by β‐elimination of a lithium halide and, stabilization of the resulting 2‐biaryllithium intermediate by <hi rend="italic">in situ</hi> transfer of bromine or iodine from the starting material. This straightforward transition metal‐free access to biaryls allows the preparation of highly valuable halobiaryls on a gram scale in excellent yields. These precursors can be subsequently functionalized by highly regioselective halogen/metal permutations into a vast variety of target molecules. This was demonstrated in the synthesis of several mono‐ and diphosphine ligands.</p></abstract><abstract xml:lang="en" style="graphical"><p><figure type="box"><media mimeType="image" url="urn:x-wiley:16154150:media:ADSC200700211:content"></media><media mimeType="image/gif" url="" rendition="webLoRes"></media><media mimeType="image/gif" url="" rendition="webOriginal"></media><media mimeType="image/gif" url="" rendition="webHiRes"></media></figure></p></abstract><textClass><keywords xml:lang="en"><term xml:id="kwd1">arynes</term><term xml:id="kwd2">biaryls</term><term xml:id="kwd3">CC coupling</term><term xml:id="kwd4">halogen/metal exchange</term><term xml:id="kwd5">phosphines</term></keywords><keywords rend="articleCategory"><term>Update</term></keywords><keywords rend="tocHeading1"><term>Updates</term></keywords></textClass><langUsage><language ident="en"></language></langUsage></profileDesc></teiHeader></istex:fulltextTEI><json:item><extension>txt</extension><original>false</original><mimetype>text/plain</mimetype><uri>https://api.istex.fr/document/252E46DC67C2FC99E026E4362FC0A53AA2FD6591/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Wiley, elements deleted: body"><istex:xmlDeclaration>version="1.0" encoding="UTF-8" standalone="yes"</istex:xmlDeclaration><istex:document><component version="2.0" type="serialArticle" xml:lang="en"><header><publicationMeta level="product"><publisherInfo><publisherName>WILEY‐VCH Verlag</publisherName><publisherLoc>Weinheim</publisherLoc></publisherInfo><doi registered="yes">10.1002/(ISSN)1615-4169</doi><issn type="print">1615-4150</issn><issn type="electronic">1615-4169</issn><idGroup><id type="product" value="ADSC"></id></idGroup><titleGroup><title type="main" xml:lang="en" sort="ADVANCED SYNTHESIS CATALYSIS">Advanced Synthesis & Catalysis</title><title type="short">Adv. 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Catal.</title></titleGroup><selfCitationGroup><citation type="ancestor" xml:id="cit1"><journalTitle>Journal für praktische Chemie</journalTitle><accessionId ref="info:x-wiley/issn/14369966">1436-9966</accessionId><pubYear year="2000">2000</pubYear><vol>342</vol><issue>8</issue></citation></selfCitationGroup></publicationMeta><publicationMeta level="part" position="170"><doi origin="wiley" registered="yes">10.1002/adsc.v349:17/18</doi><titleGroup><title type="specialIssueTitle">Dedicated Cluster</title></titleGroup><numberingGroup><numbering type="journalVolume" number="349">349</numbering><numbering type="includedIssue">17</numbering><numbering type="includedIssue">18</numbering><numbering type="journalIssue">17‐18</numbering></numberingGroup><coverDate startDate="2007-12-10">December 10, 2007</coverDate></publicationMeta><publicationMeta level="unit" type="miscellaneous" position="27" status="forIssue"><doi origin="wiley" registered="yes">10.1002/adsc.200700211</doi><idGroup><id type="unit" value="ADSC200700211"></id></idGroup><countGroup><count type="pageTotal" number="9"></count></countGroup><titleGroup><title type="articleCategory">Update</title><title type="tocHeading1">Updates</title></titleGroup><copyright ownership="publisher">Copyright © 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</copyright><eventGroup><event type="manuscriptReceived" date="2007-04-26"></event><event type="manuscriptRevised" date="2007-08-13"></event><event type="firstOnline" date="2007-10-04"></event><event type="publishedOnlineFinalForm" date="2007-12-03"></event><event type="xmlConverted" agent="Converter:JWSART34_TO_WML3G version:2.3.2 mode:FullText source:HeaderRef result:HeaderRef" date="2010-03-09"></event><event type="xmlConverted" agent="Converter:WILEY_ML3G_TO_WILEY_ML3GV2 version:3.8.8" date="2014-01-01"></event><event type="xmlConverted" agent="Converter:WML3G_To_WML3G version:4.1.7 mode:FullText,remove_FC" date="2014-10-14"></event></eventGroup><numberingGroup><numbering type="pageFirst">2705</numbering><numbering type="pageLast">2713</numbering></numberingGroup><linkGroup><link type="toTypesetVersion" href="file:ADSC.ADSC200700211.pdf"></link></linkGroup></publicationMeta><contentMeta><countGroup><count type="figureTotal" number="1"></count><count type="tableTotal" number="0"></count><count type="referenceTotal" number="53"></count></countGroup><titleGroup><title type="main" xml:lang="en">A Practical Transition Metal‐Free Aryl‐Aryl Coupling Method: Arynes as Key Intermediates</title></titleGroup><creators><creator xml:id="au1" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Frédéric R.</givenNames><familyName>Leroux</familyName></personName><contactDetails><email normalForm="frederic.leroux@ecpm.u-strasbg.fr">frederic.leroux@ecpm.u‐strasbg.fr</email></contactDetails></creator><creator xml:id="au2" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Laurence</givenNames><familyName>Bonnafoux</familyName></personName></creator><creator xml:id="au3" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Christophe</givenNames><familyName>Heiss</familyName></personName></creator><creator xml:id="au4" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Françoise</givenNames><familyName>Colobert</familyName></personName></creator><creator xml:id="au5" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Don Antoine</givenNames><familyName>Lanfranchi</familyName></personName></creator></creators><affiliationGroup><affiliation xml:id="aa" countryCode="FR" type="organization"><unparsedAffiliation>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742</unparsedAffiliation></affiliation></affiliationGroup><keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">arynes</keyword><keyword xml:id="kwd2">biaryls</keyword><keyword xml:id="kwd3">CC coupling</keyword><keyword xml:id="kwd4">halogen/metal exchange</keyword><keyword xml:id="kwd5">phosphines</keyword></keywordGroup><supportingInformation><p>Supporting information for this article is available on the WWW under <url href="http://www.wiley-vch.de/contents/jc_2258/2007/d700211_s.pdf">http://www.wiley‐vch.de/contents/jc_2258/2007/d700211_s.pdf</url> or from the author.</p></supportingInformation><abstractGroup><abstract type="main" xml:lang="en"><title type="main">Abstract</title><p>Upon treatment of various aryllithium intermediates with 1,2‐dibromobenzene or 1‐bromo‐2‐iodobenzene, dissymmetrical <i>ortho,ortho′</i>‐di‐, tri‐ and even tetrasubstituted bromo‐ or iodobiaryls become readily available. The crucial steps in all these reactions were the nucleophilic addition of the organolithium precursor to a transient aryne species released from it by β‐elimination of a lithium halide and, stabilization of the resulting 2‐biaryllithium intermediate by <i>in situ</i> transfer of bromine or iodine from the starting material. This straightforward transition metal‐free access to biaryls allows the preparation of highly valuable halobiaryls on a gram scale in excellent yields. These precursors can be subsequently functionalized by highly regioselective halogen/metal permutations into a vast variety of target molecules. This was demonstrated in the synthesis of several mono‐ and diphosphine ligands.</p></abstract><abstract type="graphical" xml:lang="en"><p><blockFixed type="graphic"><mediaResourceGroup><mediaResource alt="image" eRights="yes" copyright="WILEY-VCH" href="urn:x-wiley:16154150:media:ADSC200700211:content"></mediaResource><mediaResource alt="thumbnail image" rendition="webLoRes" mimeType="image/gif" href=""></mediaResource><mediaResource alt="original image" rendition="webOriginal" mimeType="image/gif" href=""></mediaResource><mediaResource alt="magnified image" rendition="webHiRes" mimeType="image/gif" href=""></mediaResource></mediaResourceGroup></blockFixed></p></abstract></abstractGroup></contentMeta></header></component></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>A Practical Transition Metal‐Free Aryl‐Aryl Coupling Method: Arynes as Key Intermediates</title></titleInfo><titleInfo type="alternative" contentType="CDATA" lang="en"><title>A Practical Transition Metal‐Free Aryl‐Aryl Coupling Method: Arynes as Key Intermediates</title></titleInfo><name type="personal"><namePart type="given">Frédéric R.</namePart><namePart type="family">Leroux</namePart><affiliation>E-mail: frederic.leroux@ecpm.u‐strasbg.fr</affiliation><affiliation>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742</affiliation><affiliation>E-mail: frederic.leroux@ecpm.u‐strasbg.fr</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Laurence</namePart><namePart type="family">Bonnafoux</namePart><affiliation>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Christophe</namePart><namePart type="family">Heiss</namePart><affiliation>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Françoise</namePart><namePart type="family">Colobert</namePart><affiliation>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Don Antoine</namePart><namePart type="family">Lanfranchi</namePart><affiliation>Laboratoire de stéréochimie, Université Louis Pasteur (ECPM), CNRS, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France, Fax: (+33)‐(0)3‐9024‐2742</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="article" displayLabel="miscellaneous" authority="ISTEX" authorityURI="https://content-type.data.istex.fr" valueURI="https://content-type.data.istex.fr/ark:/67375/XTP-6N5SZHKN-D">article</genre><originInfo><publisher>WILEY‐VCH Verlag</publisher><place><placeTerm type="text">Weinheim</placeTerm></place><dateIssued encoding="w3cdtf">2007-12-10</dateIssued><dateCaptured encoding="w3cdtf">2007-04-26</dateCaptured><copyrightDate encoding="w3cdtf">2007</copyrightDate></originInfo><language><languageTerm type="code" authority="rfc3066">en</languageTerm><languageTerm type="code" authority="iso639-2b">eng</languageTerm></language><physicalDescription><extent unit="figures">1</extent><extent unit="tables">0</extent><extent unit="references">53</extent></physicalDescription><abstract lang="en">Upon treatment of various aryllithium intermediates with 1,2‐dibromobenzene or 1‐bromo‐2‐iodobenzene, dissymmetrical ortho,ortho′‐di‐, tri‐ and even tetrasubstituted bromo‐ or iodobiaryls become readily available. The crucial steps in all these reactions were the nucleophilic addition of the organolithium precursor to a transient aryne species released from it by β‐elimination of a lithium halide and, stabilization of the resulting 2‐biaryllithium intermediate by in situ transfer of bromine or iodine from the starting material. This straightforward transition metal‐free access to biaryls allows the preparation of highly valuable halobiaryls on a gram scale in excellent yields. These precursors can be subsequently functionalized by highly regioselective halogen/metal permutations into a vast variety of target molecules. This was demonstrated in the synthesis of several mono‐ and diphosphine ligands.</abstract><abstract type="graphical" lang="en"></abstract><subject lang="en"><genre>keywords</genre><topic>arynes</topic><topic>biaryls</topic><topic>CC coupling</topic><topic>halogen/metal exchange</topic><topic>phosphines</topic></subject><relatedItem type="host"><titleInfo><title>Advanced Synthesis & Catalysis</title></titleInfo><titleInfo type="abbreviated"><title>Adv. Synth. 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