Survey of Synthetic Approaches to Natural (Peyssonenynes) and Unnatural Acetoxyenediynes
Identifieur interne : 001578 ( Istex/Corpus ); précédent : 001577; suivant : 001579Survey of Synthetic Approaches to Natural (Peyssonenynes) and Unnatural Acetoxyenediynes
Auteurs : Patricia García-Domínguez ; Rosana Alvarez ; Ángel R. De LeraSource :
- European Journal of Organic Chemistry [ 1434-193X ] ; 2012-09.
English descriptors
- KwdEn :
- Ac2o, Acetate, Acetic, Acetic anhydride, Acetoxyenediyne, Acetoxyenediynes, Acetoxyenyne, Acetoxyenynes, Alkyne, Amide, Angew, Anhydride, Anion, Aqueous solution, Brine, Calcd, Carbonate, Cdcl3, Chem, Colorless, Column chromatography, Deprotection, Diyne, Diynyl, Diynyl anion, Dmap, Dropwise, Enol, Enol acetate, Enol acetates, Ester, Et2o, Et3n, Ether, Etoac, Further purification, General procedure, Gmbh, Hexane, Hplc, Hrms, Iodoalkyne, Ipr3si, Isomer, Ketone, Kgaa, Lera, Lett, Lhmds, Lithium, Meoh, Mmol, Model system, Nacl, Natural products, Nbu4nf, Nbuli, Next step, Nh4cl, Organic layers, Palmitic acid, Peyssonenynes, Piperidine, Potassium carbonate, Propargylic, Propargylic ketone, Propargylic ketones, Purification, Reaction mixture, Reagent, Room temperature, Silica, Sonogashira, Tbaf, Terminal alkynes, Tetrahedron, Tetrahedron lett, Title compound, Title product, Tmeda, Unnatural acetoxyenediynes, Unsymmetrical, Verlag, Verlag gmbh, Weinheim, Weinreb, Weinreb amide.
- Teeft :
- Ac2o, Acetate, Acetic, Acetic anhydride, Acetoxyenediyne, Acetoxyenediynes, Acetoxyenyne, Acetoxyenynes, Alkyne, Amide, Angew, Anhydride, Anion, Aqueous solution, Brine, Calcd, Carbonate, Cdcl3, Chem, Colorless, Column chromatography, Deprotection, Diyne, Diynyl, Diynyl anion, Dmap, Dropwise, Enol, Enol acetate, Enol acetates, Ester, Et2o, Et3n, Ether, Etoac, Further purification, General procedure, Gmbh, Hexane, Hplc, Hrms, Iodoalkyne, Ipr3si, Isomer, Ketone, Kgaa, Lera, Lett, Lhmds, Lithium, Meoh, Mmol, Model system, Nacl, Natural products, Nbu4nf, Nbuli, Next step, Nh4cl, Organic layers, Palmitic acid, Peyssonenynes, Piperidine, Potassium carbonate, Propargylic, Propargylic ketone, Propargylic ketones, Purification, Reaction mixture, Reagent, Room temperature, Silica, Sonogashira, Tbaf, Terminal alkynes, Tetrahedron, Tetrahedron lett, Title compound, Title product, Tmeda, Unnatural acetoxyenediynes, Unsymmetrical, Verlag, Verlag gmbh, Weinheim, Weinreb, Weinreb amide.
Abstract
Four convergent synthetic approaches to acetoxyenediynes have been explored to gain access to peyssonenynes A and B, which are natural products isolated from the red alga Peyssonelia caulifera. After optimization of the routes with a palmitic acid based model system, the synthesis of the peyssonenynes was completed by using, as the key steps, 1) Ni/Cu co‐catalyzed cross‐coupling of terminal alkynes, 2) Sonogashira cross‐coupling, 3) the addition of a diynyl anion to a Weinreb amide, and 4) the previously reported Cadiot–Chodkiewicz cross‐coupling reaction. Because bulky amide bases stereoselectively provided the (E)‐ and (Z)‐acetoxyenynes from the precursor ynones, the cross‐coupling routes to obtaining the acetoxyenediynes by using these stereochemically homogeneous intermediates are comparable to the alternatives in which enolacetate formation of the acetoxyenediyne motif takes place at a late stage in the synthesis.
Url:
DOI: 10.1002/ejoc.201200246
Links to Exploration step
ISTEX:C7FC948F3AA8E591951ADC12AF18D0A9829AFE8ELe document en format XML
<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title xml:lang="en">Survey of Synthetic Approaches to Natural (Peyssonenynes) and Unnatural Acetoxyenediynes</title><author><name sortKey="Garcia Ominguez, Patricia" sort="Garcia Ominguez, Patricia" uniqKey="Garcia Ominguez P" first="Patricia" last="García-Domínguez">Patricia García-Domínguez</name><affiliation><mods:affiliation>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622</mods:affiliation></affiliation></author><author><name sortKey="Alvarez, Rosana" sort="Alvarez, Rosana" uniqKey="Alvarez R" first="Rosana" last="Alvarez">Rosana Alvarez</name><affiliation><mods:affiliation>E-mail: rar@uvigo.es</mods:affiliation></affiliation><affiliation><mods:affiliation>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: rar@uvigo.es</mods:affiliation></affiliation></author><author><name sortKey="De Lera, Angel R" sort="De Lera, Angel R" uniqKey="De Lera A" first="Ángel R." last="De Lera">Ángel R. De Lera</name><affiliation><mods:affiliation>E-mail: qolera@uvigo.es</mods:affiliation></affiliation><affiliation><mods:affiliation>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: qolera@uvigo.es</mods:affiliation></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:C7FC948F3AA8E591951ADC12AF18D0A9829AFE8E</idno><date when="2012" year="2012">2012</date><idno type="doi">10.1002/ejoc.201200246</idno><idno type="url">https://api.istex.fr/document/C7FC948F3AA8E591951ADC12AF18D0A9829AFE8E/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">001578</idno><idno type="wicri:explorRef" wicri:stream="Istex" wicri:step="Corpus" wicri:corpus="ISTEX">001578</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a" type="main" xml:lang="en">Survey of Synthetic Approaches to Natural (Peyssonenynes) and Unnatural Acetoxyenediynes<ref type="figure" target="#f1"></ref></title><author><name sortKey="Garcia Ominguez, Patricia" sort="Garcia Ominguez, Patricia" uniqKey="Garcia Ominguez P" first="Patricia" last="García-Domínguez">Patricia García-Domínguez</name><affiliation><mods:affiliation>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622</mods:affiliation></affiliation></author><author><name sortKey="Alvarez, Rosana" sort="Alvarez, Rosana" uniqKey="Alvarez R" first="Rosana" last="Alvarez">Rosana Alvarez</name><affiliation><mods:affiliation>E-mail: rar@uvigo.es</mods:affiliation></affiliation><affiliation><mods:affiliation>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: rar@uvigo.es</mods:affiliation></affiliation></author><author><name sortKey="De Lera, Angel R" sort="De Lera, Angel R" uniqKey="De Lera A" first="Ángel R." last="De Lera">Ángel R. De Lera</name><affiliation><mods:affiliation>E-mail: qolera@uvigo.es</mods:affiliation></affiliation><affiliation><mods:affiliation>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: qolera@uvigo.es</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j" type="main">European Journal of Organic Chemistry</title><title level="j" type="alt">EUROPEAN JOURNAL OF ORGANIC CHEMISTRY</title><idno type="ISSN">1434-193X</idno><idno type="eISSN">1099-0690</idno><imprint><biblScope unit="vol">2012</biblScope><biblScope unit="issue">25</biblScope><biblScope unit="page" from="4762">4762</biblScope><biblScope unit="page" to="4782">4782</biblScope><biblScope unit="page-count">21</biblScope><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2012-09">2012-09</date></imprint><idno type="ISSN">1434-193X</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">1434-193X</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Ac2o</term><term>Acetate</term><term>Acetic</term><term>Acetic anhydride</term><term>Acetoxyenediyne</term><term>Acetoxyenediynes</term><term>Acetoxyenyne</term><term>Acetoxyenynes</term><term>Alkyne</term><term>Amide</term><term>Angew</term><term>Anhydride</term><term>Anion</term><term>Aqueous solution</term><term>Brine</term><term>Calcd</term><term>Carbonate</term><term>Cdcl3</term><term>Chem</term><term>Colorless</term><term>Column chromatography</term><term>Deprotection</term><term>Diyne</term><term>Diynyl</term><term>Diynyl anion</term><term>Dmap</term><term>Dropwise</term><term>Enol</term><term>Enol acetate</term><term>Enol acetates</term><term>Ester</term><term>Et2o</term><term>Et3n</term><term>Ether</term><term>Etoac</term><term>Further purification</term><term>General procedure</term><term>Gmbh</term><term>Hexane</term><term>Hplc</term><term>Hrms</term><term>Iodoalkyne</term><term>Ipr3si</term><term>Isomer</term><term>Ketone</term><term>Kgaa</term><term>Lera</term><term>Lett</term><term>Lhmds</term><term>Lithium</term><term>Meoh</term><term>Mmol</term><term>Model system</term><term>Nacl</term><term>Natural products</term><term>Nbu4nf</term><term>Nbuli</term><term>Next step</term><term>Nh4cl</term><term>Organic layers</term><term>Palmitic acid</term><term>Peyssonenynes</term><term>Piperidine</term><term>Potassium carbonate</term><term>Propargylic</term><term>Propargylic ketone</term><term>Propargylic ketones</term><term>Purification</term><term>Reaction mixture</term><term>Reagent</term><term>Room temperature</term><term>Silica</term><term>Sonogashira</term><term>Tbaf</term><term>Terminal alkynes</term><term>Tetrahedron</term><term>Tetrahedron lett</term><term>Title compound</term><term>Title product</term><term>Tmeda</term><term>Unnatural acetoxyenediynes</term><term>Unsymmetrical</term><term>Verlag</term><term>Verlag gmbh</term><term>Weinheim</term><term>Weinreb</term><term>Weinreb amide</term></keywords><keywords scheme="Teeft" xml:lang="en"><term>Ac2o</term><term>Acetate</term><term>Acetic</term><term>Acetic anhydride</term><term>Acetoxyenediyne</term><term>Acetoxyenediynes</term><term>Acetoxyenyne</term><term>Acetoxyenynes</term><term>Alkyne</term><term>Amide</term><term>Angew</term><term>Anhydride</term><term>Anion</term><term>Aqueous solution</term><term>Brine</term><term>Calcd</term><term>Carbonate</term><term>Cdcl3</term><term>Chem</term><term>Colorless</term><term>Column chromatography</term><term>Deprotection</term><term>Diyne</term><term>Diynyl</term><term>Diynyl anion</term><term>Dmap</term><term>Dropwise</term><term>Enol</term><term>Enol acetate</term><term>Enol acetates</term><term>Ester</term><term>Et2o</term><term>Et3n</term><term>Ether</term><term>Etoac</term><term>Further purification</term><term>General procedure</term><term>Gmbh</term><term>Hexane</term><term>Hplc</term><term>Hrms</term><term>Iodoalkyne</term><term>Ipr3si</term><term>Isomer</term><term>Ketone</term><term>Kgaa</term><term>Lera</term><term>Lett</term><term>Lhmds</term><term>Lithium</term><term>Meoh</term><term>Mmol</term><term>Model system</term><term>Nacl</term><term>Natural products</term><term>Nbu4nf</term><term>Nbuli</term><term>Next step</term><term>Nh4cl</term><term>Organic layers</term><term>Palmitic acid</term><term>Peyssonenynes</term><term>Piperidine</term><term>Potassium carbonate</term><term>Propargylic</term><term>Propargylic ketone</term><term>Propargylic ketones</term><term>Purification</term><term>Reaction mixture</term><term>Reagent</term><term>Room temperature</term><term>Silica</term><term>Sonogashira</term><term>Tbaf</term><term>Terminal alkynes</term><term>Tetrahedron</term><term>Tetrahedron lett</term><term>Title compound</term><term>Title product</term><term>Tmeda</term><term>Unnatural acetoxyenediynes</term><term>Unsymmetrical</term><term>Verlag</term><term>Verlag gmbh</term><term>Weinheim</term><term>Weinreb</term><term>Weinreb amide</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Four convergent synthetic approaches to acetoxyenediynes have been explored to gain access to peyssonenynes A and B, which are natural products isolated from the red alga Peyssonelia caulifera. After optimization of the routes with a palmitic acid based model system, the synthesis of the peyssonenynes was completed by using, as the key steps, 1) Ni/Cu co‐catalyzed cross‐coupling of terminal alkynes, 2) Sonogashira cross‐coupling, 3) the addition of a diynyl anion to a Weinreb amide, and 4) the previously reported Cadiot–Chodkiewicz cross‐coupling reaction. Because bulky amide bases stereoselectively provided the (E)‐ and (Z)‐acetoxyenynes from the precursor ynones, the cross‐coupling routes to obtaining the acetoxyenediynes by using these stereochemically homogeneous intermediates are comparable to the alternatives in which enolacetate formation of the acetoxyenediyne motif takes place at a late stage in the synthesis.</div></front></TEI><istex><corpusName>wiley</corpusName><keywords><teeft><json:string>mmol</json:string><json:string>chem</json:string><json:string>cdcl3</json:string><json:string>column chromatography</json:string><json:string>isomer</json:string><json:string>general procedure</json:string><json:string>nacl</json:string><json:string>hrms</json:string><json:string>calcd</json:string><json:string>meoh</json:string><json:string>enol</json:string><json:string>title compound</json:string><json:string>weinheim</json:string><json:string>title product</json:string><json:string>aqueous solution</json:string><json:string>verlag</json:string><json:string>gmbh</json:string><json:string>verlag gmbh</json:string><json:string>kgaa</json:string><json:string>room temperature</json:string><json:string>anhydride</json:string><json:string>acetic</json:string><json:string>deprotection</json:string><json:string>propargylic</json:string><json:string>alkyne</json:string><json:string>enol acetates</json:string><json:string>acetic anhydride</json:string><json:string>organic layers</json:string><json:string>peyssonenynes</json:string><json:string>acetoxyenediynes</json:string><json:string>lera</json:string><json:string>et3n</json:string><json:string>ac2o</json:string><json:string>dmap</json:string><json:string>reaction mixture</json:string><json:string>etoac</json:string><json:string>ketone</json:string><json:string>tetrahedron</json:string><json:string>ipr3si</json:string><json:string>silica</json:string><json:string>ester</json:string><json:string>lithium</json:string><json:string>tmeda</json:string><json:string>et2o</json:string><json:string>model system</json:string><json:string>dropwise</json:string><json:string>brine</json:string><json:string>piperidine</json:string><json:string>weinreb</json:string><json:string>hexane</json:string><json:string>potassium carbonate</json:string><json:string>carbonate</json:string><json:string>lett</json:string><json:string>hplc</json:string><json:string>natural products</json:string><json:string>diyne</json:string><json:string>unnatural acetoxyenediynes</json:string><json:string>amide</json:string><json:string>unsymmetrical</json:string><json:string>sonogashira</json:string><json:string>diynyl</json:string><json:string>angew</json:string><json:string>enol acetate</json:string><json:string>lhmds</json:string><json:string>tbaf</json:string><json:string>tetrahedron lett</json:string><json:string>acetoxyenynes</json:string><json:string>nbu4nf</json:string><json:string>acetoxyenyne</json:string><json:string>nh4cl</json:string><json:string>iodoalkyne</json:string><json:string>nbuli</json:string><json:string>diynyl anion</json:string><json:string>weinreb amide</json:string><json:string>acetoxyenediyne</json:string><json:string>colorless</json:string><json:string>anion</json:string><json:string>palmitic acid</json:string><json:string>acetate</json:string><json:string>terminal alkynes</json:string><json:string>next step</json:string><json:string>further purification</json:string><json:string>propargylic ketone</json:string><json:string>propargylic ketones</json:string><json:string>purification</json:string><json:string>ether</json:string><json:string>reagent</json:string></teeft></keywords><author><json:item><name>Patricia García‐Domínguez</name><affiliations><json:string>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622</json:string></affiliations></json:item><json:item><name>Rosana Alvarez</name><affiliations><json:string>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622</json:string><json:string>E-mail: rar@uvigo.es</json:string></affiliations></json:item><json:item><name>Ángel R. de Lera</name><affiliations><json:string>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622</json:string><json:string>E-mail: qolera@uvigo.es</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>Natural products</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Total synthesis</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Synthetic methods</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Cross‐coupling</value></json:item></subject><articleId><json:string>EJOC201200246</json:string></articleId><language><json:string>eng</json:string></language><originalGenre><json:string>article</json:string></originalGenre><abstract>Four convergent synthetic approaches to acetoxyenediynes have been explored to gain access to peyssonenynes A and B, which are natural products isolated from the red alga Peyssonelia caulifera. After optimization of the routes with a palmitic acid based model system, the synthesis of the peyssonenynes was completed by using, as the key steps, 1) Ni/Cu co‐catalyzed cross‐coupling of terminal alkynes, 2) Sonogashira cross‐coupling, 3) the addition of a diynyl anion to a Weinreb amide, and 4) the previously reported Cadiot–Chodkiewicz cross‐coupling reaction. Because bulky amide bases stereoselectively provided the (E)‐ and (Z)‐acetoxyenynes from the precursor ynones, the cross‐coupling routes to obtaining the acetoxyenediynes by using these stereochemically homogeneous intermediates are comparable to the alternatives in which enolacetate formation of the acetoxyenediyne motif takes place at a late stage in the synthesis.</abstract><qualityIndicators><score>6.572</score><pdfVersion>1.3</pdfVersion><pdfPageSize>594.92 x 793.94 pts</pdfPageSize><refBibsNative>true</refBibsNative><abstractCharCount>932</abstractCharCount><pdfWordCount>18579</pdfWordCount><pdfCharCount>102071</pdfCharCount><pdfPageCount>21</pdfPageCount><abstractWordCount>131</abstractWordCount></qualityIndicators><title>Survey of Synthetic Approaches to Natural (Peyssonenynes) and Unnatural Acetoxyenediynes</title><genre><json:string>article</json:string></genre><host><title>European Journal of Organic Chemistry</title><language><json:string>unknown</json:string></language><doi><json:string>10.1002/(ISSN)1099-0690</json:string></doi><issn><json:string>1434-193X</json:string></issn><eissn><json:string>1099-0690</json:string></eissn><publisherId><json:string>EJOC</json:string></publisherId><volume>2012</volume><issue>25</issue><pages><first>4762</first><last>4782</last><total>21</total></pages><genre><json:string>journal</json:string></genre><subject><json:item><value>Full Paper</value></json:item></subject></host><categories><wos><json:string>science</json:string><json:string>chemistry, organic</json:string></wos><scienceMetrix><json:string>natural sciences</json:string><json:string>chemistry</json:string><json:string>organic chemistry</json:string></scienceMetrix></categories><publicationDate>2012</publicationDate><copyrightDate>2012</copyrightDate><doi><json:string>10.1002/ejoc.201200246</json:string></doi><id>C7FC948F3AA8E591951ADC12AF18D0A9829AFE8E</id><score>1</score><fulltext><json:item><extension>pdf</extension><original>true</original><mimetype>application/pdf</mimetype><uri>https://api.istex.fr/document/C7FC948F3AA8E591951ADC12AF18D0A9829AFE8E/fulltext/pdf</uri></json:item><json:item><extension>zip</extension><original>false</original><mimetype>application/zip</mimetype><uri>https://api.istex.fr/document/C7FC948F3AA8E591951ADC12AF18D0A9829AFE8E/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/C7FC948F3AA8E591951ADC12AF18D0A9829AFE8E/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a" type="main" xml:lang="en">Survey of Synthetic Approaches to Natural (Peyssonenynes) and Unnatural Acetoxyenediynes<ref type="figure" target="#f1"></ref></title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><availability><licence>Copyright © 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</licence></availability><date type="published" when="2012-09"></date></publicationStmt><notesStmt><note type="content-type" subtype="article" source="article" scheme="https://content-type.data.istex.fr/ark:/67375/XTP-6N5SZHKN-D">article</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="article"><analytic><title level="a" type="main" xml:lang="en">Survey of Synthetic Approaches to Natural (Peyssonenynes) and Unnatural Acetoxyenediynes<ref type="figure" target="#f1"></ref></title><title level="a" type="short" xml:lang="en">Syntheses of Natural and Unnatural Acetoxyenediynes</title><author xml:id="author-0000"><persName><forename type="first">Patricia</forename><surname>García‐Domínguez</surname></persName><affiliation>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622<address><country key="ES"></country></address></affiliation></author><author xml:id="author-0001"><persName><forename type="first">Rosana</forename><surname>Alvarez</surname></persName><email>rar@uvigo.es</email><affiliation>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622<address><country key="ES"></country></address></affiliation></author><author xml:id="author-0002"><persName><forename type="first">Ángel R.</forename><surname>de Lera</surname></persName><email>qolera@uvigo.es</email><affiliation>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622<address><country key="ES"></country></address></affiliation></author><idno type="istex">C7FC948F3AA8E591951ADC12AF18D0A9829AFE8E</idno><idno type="ark">ark:/67375/WNG-QZL7NN18-Z</idno><idno type="DOI">10.1002/ejoc.201200246</idno><idno type="unit">EJOC201200246</idno><idno type="toTypesetVersion">file:EJOC.EJOC201200246.pdf</idno></analytic><monogr><title level="j" type="main">European Journal of Organic Chemistry</title><title level="j" type="alt">EUROPEAN JOURNAL OF ORGANIC CHEMISTRY</title><idno type="pISSN">1434-193X</idno><idno type="eISSN">1099-0690</idno><idno type="book-DOI">10.1002/(ISSN)1099-0690</idno><idno type="book-part-DOI">10.1002/ejoc.v2012.25</idno><idno type="product">EJOC</idno><imprint><biblScope unit="vol">2012</biblScope><biblScope unit="issue">25</biblScope><biblScope unit="page" from="4762">4762</biblScope><biblScope unit="page" to="4782">4782</biblScope><biblScope unit="page-count">21</biblScope><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2012-09"></date></imprint></monogr></biblStruct></sourceDesc></fileDesc><profileDesc><abstract xml:lang="en" style="main"><head>Abstract</head><p>Four convergent synthetic approaches to acetoxyenediynes have been explored to gain access to peyssonenynes A and B, which are natural products isolated from the red alga <hi rend="italic">Peyssonelia caulifera</hi>. After optimization of the routes with a palmitic acid based model system, the synthesis of the peyssonenynes was completed by using, as the key steps, 1) Ni/Cu co‐catalyzed cross‐coupling of terminal alkynes, 2) Sonogashira cross‐coupling, 3) the addition of a diynyl anion to a Weinreb amide, and 4) the previously reported Cadiot–Chodkiewicz cross‐coupling reaction. Because bulky amide bases stereoselectively provided the (<hi rend="italic">E</hi>)‐ and (<hi rend="italic">Z</hi>)‐acetoxyenynes from the precursor ynones, the cross‐coupling routes to obtaining the acetoxyenediynes by using these stereochemically homogeneous intermediates are comparable to the alternatives in which enolacetate formation of the acetoxyenediyne motif takes place at a late stage in the synthesis.</p></abstract><abstract xml:lang="en" style="graphical"><p>Four convergent synthetic approaches to peyssonenynes have been developed after a previous optimization with a palmitic acid based model system.
<figure type="box"><media mimeType="image" url="urn:x-wiley:1434193X:media:EJOC201200246:fig000"></media></figure></p></abstract><textClass><keywords xml:lang="en"><term xml:id="kwd1">Natural products</term><term xml:id="kwd2">Total synthesis</term><term xml:id="kwd3">Synthetic methods</term><term xml:id="kwd4">Cross‐coupling</term></keywords><keywords rend="articleCategory"><term>Full Paper</term></keywords><keywords rend="tocHeading1"><term>Full Papers</term></keywords><keywords rend="tocHeading2"><term>Natural Product Synthesis</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/C7FC948F3AA8E591951ADC12AF18D0A9829AFE8E/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)1099-0690</doi><issn type="print">1434-193X</issn><issn type="electronic">1099-0690</issn><idGroup><id type="product" value="EJOC"></id></idGroup><titleGroup><title type="main" xml:lang="en" sort="EUROPEAN JOURNAL OF ORGANIC CHEMISTRY">European Journal of Organic Chemistry</title><title type="short">Eur. J. Org. Chem.</title></titleGroup></publicationMeta><publicationMeta level="part" position="250"><doi origin="wiley" registered="yes">10.1002/ejoc.v2012.25</doi><numberingGroup><numbering type="journalVolume" number="2012">2012</numbering><numbering type="journalIssue">25</numbering></numberingGroup><coverDate startDate="2012-09">September 2012</coverDate></publicationMeta><publicationMeta level="unit" type="article" position="16" status="forIssue"><doi origin="wiley" registered="yes">10.1002/ejoc.201200246</doi><idGroup><id type="unit" value="EJOC201200246"></id></idGroup><countGroup><count type="pageTotal" number="21"></count></countGroup><titleGroup><title type="articleCategory">Full Paper</title><title type="tocHeading1">Full Papers</title><title type="tocHeading2">Natural Product Synthesis</title></titleGroup><copyright ownership="publisher">Copyright © 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</copyright><eventGroup><event type="manuscriptReceived" date="2012-03-02"></event><event type="xmlConverted" agent="Converter:JWSART34_TO_WML3G version:3.1.6 mode:FullText mathml2tex" date="2012-08-21"></event><event type="publishedOnlineEarlyUnpaginated" date="2012-07-13"></event><event type="firstOnline" date="2012-07-13"></event><event type="publishedOnlineFinalForm" date="2012-08-21"></event><event type="xmlConverted" agent="Converter:WILEY_ML3G_TO_WILEY_ML3GV2 version:3.8.8" date="2014-01-24"></event><event type="xmlConverted" agent="Converter:WML3G_To_WML3G version:4.3.4 mode:FullText" date="2015-02-24"></event></eventGroup><numberingGroup><numbering type="pageFirst">4762</numbering><numbering type="pageLast">4782</numbering></numberingGroup><objectNameGroup><objectName elementName="figure">Scheme</objectName></objectNameGroup><linkGroup><link type="toTypesetVersion" href="file:EJOC.EJOC201200246.pdf"></link></linkGroup></publicationMeta><contentMeta><countGroup><count type="figureTotal" number="10"></count><count type="tableTotal" number="2"></count><count type="referenceTotal" number="47"></count></countGroup><titleGroup><title type="main" xml:lang="en">Survey of Synthetic Approaches to Natural (Peyssonenynes) and Unnatural Acetoxyenediynes<link href="#f1"></link></title><title type="short" xml:lang="en">Syntheses of Natural and Unnatural Acetoxyenediynes</title></titleGroup><creators><creator xml:id="au1" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Patricia</givenNames><familyName>García‐Domínguez</familyName></personName></creator><creator xml:id="au2" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Rosana</givenNames><familyName>Alvarez</familyName></personName><contactDetails><email>rar@uvigo.es</email></contactDetails></creator><creator xml:id="au3" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Ángel R.</givenNames><familyName>de Lera</familyName></personName><contactDetails><email>qolera@uvigo.es</email></contactDetails></creator></creators><affiliationGroup><affiliation xml:id="af1" countryCode="ES" type="organization"><unparsedAffiliation>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622</unparsedAffiliation></affiliation></affiliationGroup><keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">Natural products</keyword><keyword xml:id="kwd2">Total synthesis</keyword><keyword xml:id="kwd3">Synthetic methods</keyword><keyword xml:id="kwd4">Cross‐coupling</keyword></keywordGroup><fundingInfo><fundingAgency>European Union (EU)</fundingAgency><fundingNumber>LSHC‐CT‐2005‐518417</fundingNumber></fundingInfo><fundingInfo><fundingAgency>Ministerio de Economía y Competitividad</fundingAgency><fundingNumber>SAF2010‐17935‐FEDER</fundingNumber></fundingInfo><fundingInfo><fundingAgency>Xunta de Galicia</fundingAgency><fundingNumber>08CSA052383PR</fundingNumber></fundingInfo><supportingInformation><p>Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer‐reviewed, but not copy‐edited or typeset. They are made available as submitted by the authors.
</p><supportingInfoItem><mediaResource alt="supporting information" href="urn-x:wiley:1434193X:media:ejoc201200246:ejoc_201200246_sm_miscellaneous_information"></mediaResource><caption>miscellaneous_information</caption></supportingInfoItem></supportingInformation><abstractGroup><abstract type="main" xml:lang="en"><title type="main">Abstract</title><p>Four convergent synthetic approaches to acetoxyenediynes have been explored to gain access to peyssonenynes A and B, which are natural products isolated from the red alga <i>Peyssonelia caulifera</i>. After optimization of the routes with a palmitic acid based model system, the synthesis of the peyssonenynes was completed by using, as the key steps, 1) Ni/Cu co‐catalyzed cross‐coupling of terminal alkynes, 2) Sonogashira cross‐coupling, 3) the addition of a diynyl anion to a Weinreb amide, and 4) the previously reported Cadiot–Chodkiewicz cross‐coupling reaction. Because bulky amide bases stereoselectively provided the (<i>E</i>)‐ and (<i>Z</i>)‐acetoxyenynes from the precursor ynones, the cross‐coupling routes to obtaining the acetoxyenediynes by using these stereochemically homogeneous intermediates are comparable to the alternatives in which enolacetate formation of the acetoxyenediyne motif takes place at a late stage in the synthesis.</p></abstract><abstract type="graphical" xml:lang="en"><p>Four convergent synthetic approaches to peyssonenynes have been developed after a previous optimization with a palmitic acid based model system.
<blockFixed type="graphic"><mediaResourceGroup><mediaResource alt="image" eRights="yes" copyright="WILEY-VCH" href="urn:x-wiley:1434193X:media:EJOC201200246:fig000"></mediaResource></mediaResourceGroup></blockFixed></p></abstract></abstractGroup></contentMeta><noteGroup><note xml:id="f1"><p>Dedicated to Professor Patxi Palacios on the occassion of his 60th birthday</p></note></noteGroup></header></component></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>Survey of Synthetic Approaches to Natural (Peyssonenynes) and Unnatural Acetoxyenediynes</title></titleInfo><titleInfo type="abbreviated" lang="en"><title>Syntheses of Natural and Unnatural Acetoxyenediynes</title></titleInfo><titleInfo type="alternative" contentType="CDATA" lang="en"><title>Survey of Synthetic Approaches to Natural (Peyssonenynes) and Unnatural Acetoxyenediynes</title></titleInfo><name type="personal"><namePart type="given">Patricia</namePart><namePart type="family">García‐Domínguez</namePart><affiliation>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Rosana</namePart><namePart type="family">Alvarez</namePart><affiliation>E-mail: rar@uvigo.es</affiliation><affiliation>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622</affiliation><affiliation>E-mail: rar@uvigo.es</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Ángel R.</namePart><namePart type="family">de Lera</namePart><affiliation>E-mail: qolera@uvigo.es</affiliation><affiliation>Departamento de Química Orgánica, Facultade de Química, Universidade de Vigo, 36310 Vigo, Spain, Fax: +34‐986‐818622</affiliation><affiliation>E-mail: qolera@uvigo.es</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="article" displayLabel="article" 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">2012-09</dateIssued><dateCaptured encoding="w3cdtf">2012-03-02</dateCaptured><copyrightDate encoding="w3cdtf">2012</copyrightDate></originInfo><language><languageTerm type="code" authority="rfc3066">en</languageTerm><languageTerm type="code" authority="iso639-2b">eng</languageTerm></language><physicalDescription><extent unit="figures">10</extent><extent unit="tables">2</extent><extent unit="references">47</extent></physicalDescription><abstract lang="en">Four convergent synthetic approaches to acetoxyenediynes have been explored to gain access to peyssonenynes A and B, which are natural products isolated from the red alga Peyssonelia caulifera. After optimization of the routes with a palmitic acid based model system, the synthesis of the peyssonenynes was completed by using, as the key steps, 1) Ni/Cu co‐catalyzed cross‐coupling of terminal alkynes, 2) Sonogashira cross‐coupling, 3) the addition of a diynyl anion to a Weinreb amide, and 4) the previously reported Cadiot–Chodkiewicz cross‐coupling reaction. Because bulky amide bases stereoselectively provided the (E)‐ and (Z)‐acetoxyenynes from the precursor ynones, the cross‐coupling routes to obtaining the acetoxyenediynes by using these stereochemically homogeneous intermediates are comparable to the alternatives in which enolacetate formation of the acetoxyenediyne motif takes place at a late stage in the synthesis.</abstract><abstract type="graphical" lang="en">Four convergent synthetic approaches to peyssonenynes have been developed after a previous optimization with a palmitic acid based model system.</abstract><note type="content">*Dedicated to Professor Patxi Palacios on the occassion of his 60th birthday</note><note type="funding">European Union (EU) - No. LSHC‐CT‐2005‐518417; </note><note type="funding">Ministerio de Economía y Competitividad - No. SAF2010‐17935‐FEDER; </note><note type="funding">Xunta de Galicia - No. 08CSA052383PR; </note><subject lang="en"><genre>keywords</genre><topic>Natural products</topic><topic>Total synthesis</topic><topic>Synthetic methods</topic><topic>Cross‐coupling</topic></subject><relatedItem type="host"><titleInfo><title>European Journal of Organic Chemistry</title></titleInfo><titleInfo type="abbreviated"><title>Eur. J. Org. Chem.</title></titleInfo><genre type="journal" authority="ISTEX" authorityURI="https://publication-type.data.istex.fr" valueURI="https://publication-type.data.istex.fr/ark:/67375/JMC-0GLKJH51-B">journal</genre><note type="content"> Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer‐reviewed, but not copy‐edited or typeset. They are made available as submitted by the authors.Supporting Info Item: miscellaneous_information - </note><subject><genre>article-category</genre><topic>Full Paper</topic></subject><identifier type="ISSN">1434-193X</identifier><identifier type="eISSN">1099-0690</identifier><identifier type="DOI">10.1002/(ISSN)1099-0690</identifier><identifier type="PublisherID">EJOC</identifier><part><date>2012</date><detail type="volume"><caption>vol.</caption><number>2012</number></detail><detail type="issue"><caption>no.</caption><number>25</number></detail><extent unit="pages"><start>4762</start><end>4782</end><total>21</total></extent></part></relatedItem><identifier type="istex">C7FC948F3AA8E591951ADC12AF18D0A9829AFE8E</identifier><identifier type="ark">ark:/67375/WNG-QZL7NN18-Z</identifier><identifier type="DOI">10.1002/ejoc.201200246</identifier><identifier type="ArticleID">EJOC201200246</identifier><accessCondition type="use and reproduction" contentType="copyright">Copyright © 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</accessCondition><recordInfo><recordContentSource authority="ISTEX" authorityURI="https://loaded-corpus.data.istex.fr" valueURI="https://loaded-corpus.data.istex.fr/ark:/67375/XBH-L0C46X92-X">wiley</recordContentSource><recordOrigin>WILEY‐VCH Verlag</recordOrigin></recordInfo></mods><json:item><extension>json</extension><original>false</original><mimetype>application/json</mimetype><uri>https://api.istex.fr/document/C7FC948F3AA8E591951ADC12AF18D0A9829AFE8E/metadata/json</uri></json:item></metadata><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Wicri/Lorraine/explor/LrgpV1/Data/Istex/Corpus
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 001578 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/Istex/Corpus/biblio.hfd -nk 001578 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien
|wiki= Wicri/Lorraine
|area= LrgpV1
|flux= Istex
|étape= Corpus
|type= RBID
|clé= ISTEX:C7FC948F3AA8E591951ADC12AF18D0A9829AFE8E
|texte= Survey of Synthetic Approaches to Natural (Peyssonenynes) and Unnatural Acetoxyenediynes
}}
| This area was generated with Dilib version V0.6.32. |  |