Metal π-Lewis base activation in palladium(0)-catalyzed trans -alkylative cyclization of alkynals
The Pd(0)-mediated umpolung reaction of an alkyne to achieve -difunctionalization is a potential synthetic methodology, but its insightful activation mechanism of Pd(0)-alkyne interaction has yet to be established. Here, a Pd(0)-π-Lewis base activation mode is proposed and investigated by combining...
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| Veröffentlicht in: | Chemical science (Cambridge) 2024-08, Vol.15 (32), p.13032-13040 |
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| container_title | Chemical science (Cambridge) |
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| creator | Zhu, Lei Zhao, Bo Xie, Ke Gui, Wu-Tao Niu, Sheng-Li Zheng, Peng-Fei Chen, Ying-Chun Qi, Xiao-Wei Ouyang, Qin |
| description | The Pd(0)-mediated umpolung reaction of an alkyne to achieve
-difunctionalization is a potential synthetic methodology, but its insightful activation mechanism of Pd(0)-alkyne interaction has yet to be established. Here, a Pd(0)-π-Lewis base activation mode is proposed and investigated by combining theoretical and experimental studies. In this activation mode, the Pd(0) coordinates to the alkyne group and enhances its nucleophilicity through π-back-donation, facilitating the nucleophilic attack on the aldehyde to generate a
-Pd(ii)-vinyl complex. Ligand-effect studies reveal that the more electron-donating one would accelerate the reaction, and the cyclization of the challenging flexible C- or O-tethered substrates has been realized. The origin of regioselectivities is also explicated by the newly proposed metal π-Lewis base activation mode. |
| doi_str_mv | 10.1039/d4sc04190a |
| format | Article |
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-difunctionalization is a potential synthetic methodology, but its insightful activation mechanism of Pd(0)-alkyne interaction has yet to be established. Here, a Pd(0)-π-Lewis base activation mode is proposed and investigated by combining theoretical and experimental studies. In this activation mode, the Pd(0) coordinates to the alkyne group and enhances its nucleophilicity through π-back-donation, facilitating the nucleophilic attack on the aldehyde to generate a
-Pd(ii)-vinyl complex. Ligand-effect studies reveal that the more electron-donating one would accelerate the reaction, and the cyclization of the challenging flexible C- or O-tethered substrates has been realized. The origin of regioselectivities is also explicated by the newly proposed metal π-Lewis base activation mode.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/d4sc04190a</identifier><identifier>PMID: 39148807</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Aldehydes ; Alkylation ; Alkynes ; Chemistry ; Lewis base ; Palladium ; Substrates</subject><ispartof>Chemical science (Cambridge), 2024-08, Vol.15 (32), p.13032-13040</ispartof><rights>This journal is © The Royal Society of Chemistry.</rights><rights>Copyright Royal Society of Chemistry 2024</rights><rights>This journal is © The Royal Society of Chemistry 2024 The Royal Society of Chemistry</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c296t-4dbabe7fd3380fd374be421b7906bd1191bbbbf6da2ad296a6157448b4823af23</cites><orcidid>0000-0002-1161-5102 ; 0000-0002-7870-8469 ; 0000-0003-1902-0979</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/PMC11323327/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC11323327/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,723,776,780,860,881,27901,27902,53766,53768</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/39148807$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Zhu, Lei</creatorcontrib><creatorcontrib>Zhao, Bo</creatorcontrib><creatorcontrib>Xie, Ke</creatorcontrib><creatorcontrib>Gui, Wu-Tao</creatorcontrib><creatorcontrib>Niu, Sheng-Li</creatorcontrib><creatorcontrib>Zheng, Peng-Fei</creatorcontrib><creatorcontrib>Chen, Ying-Chun</creatorcontrib><creatorcontrib>Qi, Xiao-Wei</creatorcontrib><creatorcontrib>Ouyang, Qin</creatorcontrib><title>Metal π-Lewis base activation in palladium(0)-catalyzed trans -alkylative cyclization of alkynals</title><title>Chemical science (Cambridge)</title><addtitle>Chem Sci</addtitle><description>The Pd(0)-mediated umpolung reaction of an alkyne to achieve
-difunctionalization is a potential synthetic methodology, but its insightful activation mechanism of Pd(0)-alkyne interaction has yet to be established. Here, a Pd(0)-π-Lewis base activation mode is proposed and investigated by combining theoretical and experimental studies. In this activation mode, the Pd(0) coordinates to the alkyne group and enhances its nucleophilicity through π-back-donation, facilitating the nucleophilic attack on the aldehyde to generate a
-Pd(ii)-vinyl complex. Ligand-effect studies reveal that the more electron-donating one would accelerate the reaction, and the cyclization of the challenging flexible C- or O-tethered substrates has been realized. The origin of regioselectivities is also explicated by the newly proposed metal π-Lewis base activation mode.</description><subject>Aldehydes</subject><subject>Alkylation</subject><subject>Alkynes</subject><subject>Chemistry</subject><subject>Lewis base</subject><subject>Palladium</subject><subject>Substrates</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNpdkU1P20AQhleoCFCaS38AWolLQDLsl73eUxUF2iKl6qH0vJr9MCw4duq1g8Kp_5C_1A2hEWUOMyPNM6_e0SD0iZJzSri6cCJaIqgisIeOWOqyIufqw65n5BCNY7wnKTinOZMH6JArKsqSyCNkvvseavz8J5v7xxCxgegx2D6soA9tg0ODl1DX4MKwmJDTzELC10_e4b6DJuIM6od1ndiVx3Zt6_C03WsrvJk0UMePaL9KxY9f6wj9-nJ1M_uWzX98vZ5N55llqugz4QwYLyvHeUlSlsJ4waiRihTGUaqoSVEVDhi4tAEFzaUQpREl41AxPkKft7rLwSy8s75JFmu97MICurVuIej_J02407ftSlPKGedMJoXJq0LX_h587PUiROvT-Y1vh6g5UTxXuaQioSfv0Pt26DbnbihWJPuyTNTZlrJdG2Pnq50bSvTmffpS_Jy9vG-a4OO3_nfov2fxv9Auls8</recordid><startdate>20240814</startdate><enddate>20240814</enddate><creator>Zhu, Lei</creator><creator>Zhao, Bo</creator><creator>Xie, Ke</creator><creator>Gui, Wu-Tao</creator><creator>Niu, Sheng-Li</creator><creator>Zheng, Peng-Fei</creator><creator>Chen, Ying-Chun</creator><creator>Qi, Xiao-Wei</creator><creator>Ouyang, Qin</creator><general>Royal Society of Chemistry</general><general>The 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/0000-0002-1161-5102</orcidid><orcidid>https://orcid.org/0000-0002-7870-8469</orcidid><orcidid>https://orcid.org/0000-0003-1902-0979</orcidid></search><sort><creationdate>20240814</creationdate><title>Metal π-Lewis base activation in palladium(0)-catalyzed trans -alkylative cyclization of alkynals</title><author>Zhu, Lei ; Zhao, Bo ; Xie, Ke ; Gui, Wu-Tao ; Niu, Sheng-Li ; Zheng, Peng-Fei ; Chen, Ying-Chun ; Qi, Xiao-Wei ; Ouyang, Qin</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c296t-4dbabe7fd3380fd374be421b7906bd1191bbbbf6da2ad296a6157448b4823af23</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Aldehydes</topic><topic>Alkylation</topic><topic>Alkynes</topic><topic>Chemistry</topic><topic>Lewis base</topic><topic>Palladium</topic><topic>Substrates</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zhu, Lei</creatorcontrib><creatorcontrib>Zhao, Bo</creatorcontrib><creatorcontrib>Xie, Ke</creatorcontrib><creatorcontrib>Gui, Wu-Tao</creatorcontrib><creatorcontrib>Niu, Sheng-Li</creatorcontrib><creatorcontrib>Zheng, Peng-Fei</creatorcontrib><creatorcontrib>Chen, Ying-Chun</creatorcontrib><creatorcontrib>Qi, Xiao-Wei</creatorcontrib><creatorcontrib>Ouyang, Qin</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>Zhu, Lei</au><au>Zhao, Bo</au><au>Xie, Ke</au><au>Gui, Wu-Tao</au><au>Niu, Sheng-Li</au><au>Zheng, Peng-Fei</au><au>Chen, Ying-Chun</au><au>Qi, Xiao-Wei</au><au>Ouyang, Qin</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Metal π-Lewis base activation in palladium(0)-catalyzed trans -alkylative cyclization of alkynals</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2024-08-14</date><risdate>2024</risdate><volume>15</volume><issue>32</issue><spage>13032</spage><epage>13040</epage><pages>13032-13040</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>The Pd(0)-mediated umpolung reaction of an alkyne to achieve
-difunctionalization is a potential synthetic methodology, but its insightful activation mechanism of Pd(0)-alkyne interaction has yet to be established. Here, a Pd(0)-π-Lewis base activation mode is proposed and investigated by combining theoretical and experimental studies. In this activation mode, the Pd(0) coordinates to the alkyne group and enhances its nucleophilicity through π-back-donation, facilitating the nucleophilic attack on the aldehyde to generate a
-Pd(ii)-vinyl complex. Ligand-effect studies reveal that the more electron-donating one would accelerate the reaction, and the cyclization of the challenging flexible C- or O-tethered substrates has been realized. The origin of regioselectivities is also explicated by the newly proposed metal π-Lewis base activation mode.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>39148807</pmid><doi>10.1039/d4sc04190a</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0002-1161-5102</orcidid><orcidid>https://orcid.org/0000-0002-7870-8469</orcidid><orcidid>https://orcid.org/0000-0003-1902-0979</orcidid><oa>free_for_read</oa></addata></record> |
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| source | DOAJ Directory of Open Access Journals; EZB-FREE-00999 freely available EZB journals; PubMed Central; PubMed Central Open Access |
| subjects | Aldehydes Alkylation Alkynes Chemistry Lewis base Palladium Substrates |
| title | Metal π-Lewis base activation in palladium(0)-catalyzed trans -alkylative cyclization of alkynals |
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