Nickel-catalyzed C-3 direct arylation of pyridinium ions for the synthesis of 1-azafluorenes
The direct arylation of pyridine substrates using non-precious catalysts is underdeveloped but highly desirable due to its efficiency to access important motifs while being extremely cost-effective. The first nickel-catalyzed C-3 direct arylation of pyridine derivatives to provide a new approach to...
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| Veröffentlicht in: | Chemical science (Cambridge) 2016-01, Vol.7 (8), p.5581-5586 |
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| creator | Desrosiers, Jean-Nicolas Wei, Xudong Gutierrez, Osvaldo Savoie, Jolaine Qu, Bo Zeng, Xingzhong Lee, Heewon Grinberg, Nelu Haddad, Nizar Yee, Nathan K Roschangar, Frank Song, Jinhua J Kozlowski, Marisa C Senanayake, Chris H |
| description | The direct arylation of pyridine substrates using non-precious catalysts is underdeveloped but highly desirable due to its efficiency to access important motifs while being extremely cost-effective. The first nickel-catalyzed C-3 direct arylation of pyridine derivatives to provide a new approach to valuable 1-azafluorene pharmacophore frameworks was developed. This transformation is accomplished using air-stable nickel catalyst precursors combined with phenanthroline ligands and tolerates a variety of substituents. Computational studies suggest facile oxidative addition
via
the pyridinium form, deprotonation, and a subsequent carbo-nickelation cyclization. Nickel homolysis/recombination permits isomerization to the stereochemical array needed for the final elimination.
The reactivity of pyridinium ions was utilized for the first non-precious-metal-catalyzed C-3 direct arylation and was demonstrated by mechanistic studies. |
| doi_str_mv | 10.1039/c6sc01457g |
| format | Article |
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via
the pyridinium form, deprotonation, and a subsequent carbo-nickelation cyclization. Nickel homolysis/recombination permits isomerization to the stereochemical array needed for the final elimination.
The reactivity of pyridinium ions was utilized for the first non-precious-metal-catalyzed C-3 direct arylation and was demonstrated by mechanistic studies.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/c6sc01457g</identifier><identifier>PMID: 28111599</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Arrays ; Catalysis ; Catalysts ; Chemistry ; Derivatives ; Isomerization ; Nickel ; Pyridines ; Transformations</subject><ispartof>Chemical science (Cambridge), 2016-01, Vol.7 (8), p.5581-5586</ispartof><rights>This journal is © The Royal Society of Chemistry 2016 2016</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c433t-3a4770beb7f0ac5a45376502442ae6b78590a81075c1b340dafbe3c777e9c89d3</citedby><cites>FETCH-LOGICAL-c433t-3a4770beb7f0ac5a45376502442ae6b78590a81075c1b340dafbe3c777e9c89d3</cites><orcidid>0000-0001-8151-7519</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC5245920/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC5245920/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,723,776,780,860,881,27903,27904,53769,53771</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/28111599$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Desrosiers, Jean-Nicolas</creatorcontrib><creatorcontrib>Wei, Xudong</creatorcontrib><creatorcontrib>Gutierrez, Osvaldo</creatorcontrib><creatorcontrib>Savoie, Jolaine</creatorcontrib><creatorcontrib>Qu, Bo</creatorcontrib><creatorcontrib>Zeng, Xingzhong</creatorcontrib><creatorcontrib>Lee, Heewon</creatorcontrib><creatorcontrib>Grinberg, Nelu</creatorcontrib><creatorcontrib>Haddad, Nizar</creatorcontrib><creatorcontrib>Yee, Nathan K</creatorcontrib><creatorcontrib>Roschangar, Frank</creatorcontrib><creatorcontrib>Song, Jinhua J</creatorcontrib><creatorcontrib>Kozlowski, Marisa C</creatorcontrib><creatorcontrib>Senanayake, Chris H</creatorcontrib><title>Nickel-catalyzed C-3 direct arylation of pyridinium ions for the synthesis of 1-azafluorenes</title><title>Chemical science (Cambridge)</title><addtitle>Chem Sci</addtitle><description>The direct arylation of pyridine substrates using non-precious catalysts is underdeveloped but highly desirable due to its efficiency to access important motifs while being extremely cost-effective. The first nickel-catalyzed C-3 direct arylation of pyridine derivatives to provide a new approach to valuable 1-azafluorene pharmacophore frameworks was developed. This transformation is accomplished using air-stable nickel catalyst precursors combined with phenanthroline ligands and tolerates a variety of substituents. Computational studies suggest facile oxidative addition
via
the pyridinium form, deprotonation, and a subsequent carbo-nickelation cyclization. Nickel homolysis/recombination permits isomerization to the stereochemical array needed for the final elimination.
The reactivity of pyridinium ions was utilized for the first non-precious-metal-catalyzed C-3 direct arylation and was demonstrated by mechanistic studies.</description><subject>Arrays</subject><subject>Catalysis</subject><subject>Catalysts</subject><subject>Chemistry</subject><subject>Derivatives</subject><subject>Isomerization</subject><subject>Nickel</subject><subject>Pyridines</subject><subject>Transformations</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNqNkU1LxDAQhoMoKurFu5KjCNV8Nu1FkOIXiB7UmxDSdKrRbrMmrbD-eqOrq96cywwzDy8z8yK0TckBJbw8tHm0hAqpHpbQOiOCZrnk5fKiZmQNbcX4RFJwTiVTq2iNFZRSWZbr6P7K2WfoMmsG083eoMFVxnHjAtgBmzDrzOB8j32Lp7PgGte7cYJTJ-LWBzw8Ao6zPqXo4gdEM_Nm2m70AXqIm2ilNV2Era-8ge5OT26r8-zy-uyiOr7MrOB8yLgRSpEaatUSY6URkqtcEiYEM5DXqpAlMQUlSlpac0Ea09bArVIKSluUDd9AR3Pd6VhPoLHQD8F0ehrcJJ2gvXH676R3j_rBv2rJhCwZSQJ7XwLBv4wQBz1x0ULXmR78GDUt8vSu9Ob_oFxKyfOcJXR_jtrgYwzQLjaiRH-Yp6v8pvo07yzBu79vWKDfViVgZw6EaBfTH_f5O_yDnvk</recordid><startdate>20160101</startdate><enddate>20160101</enddate><creator>Desrosiers, Jean-Nicolas</creator><creator>Wei, Xudong</creator><creator>Gutierrez, Osvaldo</creator><creator>Savoie, Jolaine</creator><creator>Qu, Bo</creator><creator>Zeng, Xingzhong</creator><creator>Lee, Heewon</creator><creator>Grinberg, Nelu</creator><creator>Haddad, Nizar</creator><creator>Yee, Nathan K</creator><creator>Roschangar, Frank</creator><creator>Song, Jinhua J</creator><creator>Kozlowski, Marisa C</creator><creator>Senanayake, Chris H</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0001-8151-7519</orcidid></search><sort><creationdate>20160101</creationdate><title>Nickel-catalyzed C-3 direct arylation of pyridinium ions for the synthesis of 1-azafluorenes</title><author>Desrosiers, Jean-Nicolas ; Wei, Xudong ; Gutierrez, Osvaldo ; Savoie, Jolaine ; Qu, Bo ; Zeng, Xingzhong ; Lee, Heewon ; Grinberg, Nelu ; Haddad, Nizar ; Yee, Nathan K ; Roschangar, Frank ; Song, Jinhua J ; Kozlowski, Marisa C ; Senanayake, Chris H</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c433t-3a4770beb7f0ac5a45376502442ae6b78590a81075c1b340dafbe3c777e9c89d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Arrays</topic><topic>Catalysis</topic><topic>Catalysts</topic><topic>Chemistry</topic><topic>Derivatives</topic><topic>Isomerization</topic><topic>Nickel</topic><topic>Pyridines</topic><topic>Transformations</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Desrosiers, Jean-Nicolas</creatorcontrib><creatorcontrib>Wei, Xudong</creatorcontrib><creatorcontrib>Gutierrez, Osvaldo</creatorcontrib><creatorcontrib>Savoie, Jolaine</creatorcontrib><creatorcontrib>Qu, Bo</creatorcontrib><creatorcontrib>Zeng, Xingzhong</creatorcontrib><creatorcontrib>Lee, Heewon</creatorcontrib><creatorcontrib>Grinberg, Nelu</creatorcontrib><creatorcontrib>Haddad, Nizar</creatorcontrib><creatorcontrib>Yee, Nathan K</creatorcontrib><creatorcontrib>Roschangar, Frank</creatorcontrib><creatorcontrib>Song, Jinhua J</creatorcontrib><creatorcontrib>Kozlowski, Marisa C</creatorcontrib><creatorcontrib>Senanayake, Chris H</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Chemical science (Cambridge)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Desrosiers, Jean-Nicolas</au><au>Wei, Xudong</au><au>Gutierrez, Osvaldo</au><au>Savoie, Jolaine</au><au>Qu, Bo</au><au>Zeng, Xingzhong</au><au>Lee, Heewon</au><au>Grinberg, Nelu</au><au>Haddad, Nizar</au><au>Yee, Nathan K</au><au>Roschangar, Frank</au><au>Song, Jinhua J</au><au>Kozlowski, Marisa C</au><au>Senanayake, Chris H</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Nickel-catalyzed C-3 direct arylation of pyridinium ions for the synthesis of 1-azafluorenes</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2016-01-01</date><risdate>2016</risdate><volume>7</volume><issue>8</issue><spage>5581</spage><epage>5586</epage><pages>5581-5586</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>The direct arylation of pyridine substrates using non-precious catalysts is underdeveloped but highly desirable due to its efficiency to access important motifs while being extremely cost-effective. The first nickel-catalyzed C-3 direct arylation of pyridine derivatives to provide a new approach to valuable 1-azafluorene pharmacophore frameworks was developed. This transformation is accomplished using air-stable nickel catalyst precursors combined with phenanthroline ligands and tolerates a variety of substituents. Computational studies suggest facile oxidative addition
via
the pyridinium form, deprotonation, and a subsequent carbo-nickelation cyclization. Nickel homolysis/recombination permits isomerization to the stereochemical array needed for the final elimination.
The reactivity of pyridinium ions was utilized for the first non-precious-metal-catalyzed C-3 direct arylation and was demonstrated by mechanistic studies.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>28111599</pmid><doi>10.1039/c6sc01457g</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0001-8151-7519</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | Arrays Catalysis Catalysts Chemistry Derivatives Isomerization Nickel Pyridines Transformations |
| title | Nickel-catalyzed C-3 direct arylation of pyridinium ions for the synthesis of 1-azafluorenes |
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