Enantio- and Z-Selective δ-Hydroarylation of Aryl-Substituted 1,3-Dienes via Rh-Catalyzed Conjugate Addition
Metal-catalyzed enantioselective conjugate arylations of electron-poor alkenes are highly selective processes for C(sp )-C(sp ) bond formation. δ-Selective hydroarylations of electron-poor 1,3-dienes are less well developed and reactions that deliver high enantioselectivity while giving single alken...
Gespeichert in:
| Veröffentlicht in: | Angewandte Chemie International Edition 2024-07, Vol.63 (31), p.e202406102 |
|---|---|
| Hauptverfasser: | , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | |
|---|---|
| container_issue | 31 |
| container_start_page | e202406102 |
| container_title | Angewandte Chemie International Edition |
| container_volume | 63 |
| creator | Kozhummal, Hima Das, Sandip Kumar Cooze, Christopher J C Lundgren, Rylan J |
| description | Metal-catalyzed enantioselective conjugate arylations of electron-poor alkenes are highly selective processes for C(sp
)-C(sp
) bond formation. δ-Selective hydroarylations of electron-poor 1,3-dienes are less well developed and reactions that deliver high enantioselectivity while giving single alkene isomer products are elusive. Here we report the Rh-catalyzed δ-arylation of aryl-substituted 1,3-dienes that gives nearly exclusive Z-1,4-addition products (generally with >95 : 5 positional and geometrical selectivity). This remote functionalization provides access to chiral diarylated alkenes from readily available precursors poised for further functionalization, including in the synthesis of bioactive molecules. Mechanistic studies suggest that protonolysis of a Rh-allyl intermediate generated by diene insertion into a Rh-aryl is the turnover limiting step and occurs by an inner-sphere proton transfer pathway. |
| doi_str_mv | 10.1002/anie.202406102 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_3056666002</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>3083196248</sourcerecordid><originalsourceid>FETCH-LOGICAL-c248t-c97908471e34e878e89060fc5e69fdf1ea168e76e9747e98d3cd8f9827bcd07a3</originalsourceid><addsrcrecordid>eNpdkUFLwzAYhoMoTqdXjxLw4sHMpGmb9DjqdMJAcHrxUrLmq2Z06WzSwfxd_g5_kxmbO_hd8oU8eXl5X4QuGB0wSqNbZQ0MIhrFNGU0OkAnLIkY4ULww7DHnBMhE9ZDp87NAy8lTY9Rj0uRcBFHJ2gxssp60xCsrMZvZAo1lN6sAP98k_Fat41q17UKhMVNhYfhQqbdzHnjOw8asxtO7gxYcHhlFH7-ILnyql5_hbe8sfPuXXnAQ63NRuIMHVWqdnC-O_vo9X70ko_J5OnhMR9OSBnF0pMyExmVsWDAY5BCgsxoSqsygTSrdMVAsVSCSCETsYBMal5qWWUyErNSU6F4H11vdZdt89mB88XCuBLqWlloOldwmqRhQiABvfqHzpuutcFdoCRnWRosBWqwpcq2ca6Fqli2ZhGiKRgtNkUUmyKKfRHhw-VOtpstQO_xv-T5Lzycg6A</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>3083196248</pqid></control><display><type>article</type><title>Enantio- and Z-Selective δ-Hydroarylation of Aryl-Substituted 1,3-Dienes via Rh-Catalyzed Conjugate Addition</title><source>Wiley Online Library All Journals</source><creator>Kozhummal, Hima ; Das, Sandip Kumar ; Cooze, Christopher J C ; Lundgren, Rylan J</creator><creatorcontrib>Kozhummal, Hima ; Das, Sandip Kumar ; Cooze, Christopher J C ; Lundgren, Rylan J</creatorcontrib><description>Metal-catalyzed enantioselective conjugate arylations of electron-poor alkenes are highly selective processes for C(sp
)-C(sp
) bond formation. δ-Selective hydroarylations of electron-poor 1,3-dienes are less well developed and reactions that deliver high enantioselectivity while giving single alkene isomer products are elusive. Here we report the Rh-catalyzed δ-arylation of aryl-substituted 1,3-dienes that gives nearly exclusive Z-1,4-addition products (generally with >95 : 5 positional and geometrical selectivity). This remote functionalization provides access to chiral diarylated alkenes from readily available precursors poised for further functionalization, including in the synthesis of bioactive molecules. Mechanistic studies suggest that protonolysis of a Rh-allyl intermediate generated by diene insertion into a Rh-aryl is the turnover limiting step and occurs by an inner-sphere proton transfer pathway.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>ISSN: 1521-3773</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202406102</identifier><identifier>PMID: 38753742</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Alkenes ; Aromatic compounds ; Chemical reactions ; Chemical synthesis ; Conjugates ; Dienes ; Enantiomers ; Substitutes</subject><ispartof>Angewandte Chemie International Edition, 2024-07, Vol.63 (31), p.e202406102</ispartof><rights>2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.</rights><rights>2024. This article is published under http://creativecommons.org/licenses/by-nc/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c248t-c97908471e34e878e89060fc5e69fdf1ea168e76e9747e98d3cd8f9827bcd07a3</cites><orcidid>0000-0002-7760-6946 ; 0009-0004-8612-6161 ; 0009-0005-6508-6081</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/38753742$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kozhummal, Hima</creatorcontrib><creatorcontrib>Das, Sandip Kumar</creatorcontrib><creatorcontrib>Cooze, Christopher J C</creatorcontrib><creatorcontrib>Lundgren, Rylan J</creatorcontrib><title>Enantio- and Z-Selective δ-Hydroarylation of Aryl-Substituted 1,3-Dienes via Rh-Catalyzed Conjugate Addition</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>Metal-catalyzed enantioselective conjugate arylations of electron-poor alkenes are highly selective processes for C(sp
)-C(sp
) bond formation. δ-Selective hydroarylations of electron-poor 1,3-dienes are less well developed and reactions that deliver high enantioselectivity while giving single alkene isomer products are elusive. Here we report the Rh-catalyzed δ-arylation of aryl-substituted 1,3-dienes that gives nearly exclusive Z-1,4-addition products (generally with >95 : 5 positional and geometrical selectivity). This remote functionalization provides access to chiral diarylated alkenes from readily available precursors poised for further functionalization, including in the synthesis of bioactive molecules. Mechanistic studies suggest that protonolysis of a Rh-allyl intermediate generated by diene insertion into a Rh-aryl is the turnover limiting step and occurs by an inner-sphere proton transfer pathway.</description><subject>Alkenes</subject><subject>Aromatic compounds</subject><subject>Chemical reactions</subject><subject>Chemical synthesis</subject><subject>Conjugates</subject><subject>Dienes</subject><subject>Enantiomers</subject><subject>Substitutes</subject><issn>1433-7851</issn><issn>1521-3773</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNpdkUFLwzAYhoMoTqdXjxLw4sHMpGmb9DjqdMJAcHrxUrLmq2Z06WzSwfxd_g5_kxmbO_hd8oU8eXl5X4QuGB0wSqNbZQ0MIhrFNGU0OkAnLIkY4ULww7DHnBMhE9ZDp87NAy8lTY9Rj0uRcBFHJ2gxssp60xCsrMZvZAo1lN6sAP98k_Fat41q17UKhMVNhYfhQqbdzHnjOw8asxtO7gxYcHhlFH7-ILnyql5_hbe8sfPuXXnAQ63NRuIMHVWqdnC-O_vo9X70ko_J5OnhMR9OSBnF0pMyExmVsWDAY5BCgsxoSqsygTSrdMVAsVSCSCETsYBMal5qWWUyErNSU6F4H11vdZdt89mB88XCuBLqWlloOldwmqRhQiABvfqHzpuutcFdoCRnWRosBWqwpcq2ca6Fqli2ZhGiKRgtNkUUmyKKfRHhw-VOtpstQO_xv-T5Lzycg6A</recordid><startdate>20240729</startdate><enddate>20240729</enddate><creator>Kozhummal, Hima</creator><creator>Das, Sandip Kumar</creator><creator>Cooze, Christopher J C</creator><creator>Lundgren, Rylan J</creator><general>Wiley Subscription Services, Inc</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-7760-6946</orcidid><orcidid>https://orcid.org/0009-0004-8612-6161</orcidid><orcidid>https://orcid.org/0009-0005-6508-6081</orcidid></search><sort><creationdate>20240729</creationdate><title>Enantio- and Z-Selective δ-Hydroarylation of Aryl-Substituted 1,3-Dienes via Rh-Catalyzed Conjugate Addition</title><author>Kozhummal, Hima ; Das, Sandip Kumar ; Cooze, Christopher J C ; Lundgren, Rylan J</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c248t-c97908471e34e878e89060fc5e69fdf1ea168e76e9747e98d3cd8f9827bcd07a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Alkenes</topic><topic>Aromatic compounds</topic><topic>Chemical reactions</topic><topic>Chemical synthesis</topic><topic>Conjugates</topic><topic>Dienes</topic><topic>Enantiomers</topic><topic>Substitutes</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kozhummal, Hima</creatorcontrib><creatorcontrib>Das, Sandip Kumar</creatorcontrib><creatorcontrib>Cooze, Christopher J C</creatorcontrib><creatorcontrib>Lundgren, Rylan J</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kozhummal, Hima</au><au>Das, Sandip Kumar</au><au>Cooze, Christopher J C</au><au>Lundgren, Rylan J</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Enantio- and Z-Selective δ-Hydroarylation of Aryl-Substituted 1,3-Dienes via Rh-Catalyzed Conjugate Addition</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2024-07-29</date><risdate>2024</risdate><volume>63</volume><issue>31</issue><spage>e202406102</spage><pages>e202406102-</pages><issn>1433-7851</issn><issn>1521-3773</issn><eissn>1521-3773</eissn><abstract>Metal-catalyzed enantioselective conjugate arylations of electron-poor alkenes are highly selective processes for C(sp
)-C(sp
) bond formation. δ-Selective hydroarylations of electron-poor 1,3-dienes are less well developed and reactions that deliver high enantioselectivity while giving single alkene isomer products are elusive. Here we report the Rh-catalyzed δ-arylation of aryl-substituted 1,3-dienes that gives nearly exclusive Z-1,4-addition products (generally with >95 : 5 positional and geometrical selectivity). This remote functionalization provides access to chiral diarylated alkenes from readily available precursors poised for further functionalization, including in the synthesis of bioactive molecules. Mechanistic studies suggest that protonolysis of a Rh-allyl intermediate generated by diene insertion into a Rh-aryl is the turnover limiting step and occurs by an inner-sphere proton transfer pathway.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>38753742</pmid><doi>10.1002/anie.202406102</doi><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-7760-6946</orcidid><orcidid>https://orcid.org/0009-0004-8612-6161</orcidid><orcidid>https://orcid.org/0009-0005-6508-6081</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1433-7851 |
| ispartof | Angewandte Chemie International Edition, 2024-07, Vol.63 (31), p.e202406102 |
| issn | 1433-7851 1521-3773 1521-3773 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_3056666002 |
| source | Wiley Online Library All Journals |
| subjects | Alkenes Aromatic compounds Chemical reactions Chemical synthesis Conjugates Dienes Enantiomers Substitutes |
| title | Enantio- and Z-Selective δ-Hydroarylation of Aryl-Substituted 1,3-Dienes via Rh-Catalyzed Conjugate Addition |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-05T22%3A20%3A21IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Enantio-%20and%20Z-Selective%20%CE%B4-Hydroarylation%20of%20Aryl-Substituted%201,3-Dienes%20via%20Rh-Catalyzed%20Conjugate%20Addition&rft.jtitle=Angewandte%20Chemie%20International%20Edition&rft.au=Kozhummal,%20Hima&rft.date=2024-07-29&rft.volume=63&rft.issue=31&rft.spage=e202406102&rft.pages=e202406102-&rft.issn=1433-7851&rft.eissn=1521-3773&rft_id=info:doi/10.1002/anie.202406102&rft_dat=%3Cproquest_cross%3E3083196248%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=3083196248&rft_id=info:pmid/38753742&rfr_iscdi=true |