Bioinspired and Ligand‐Regulated Unnatural Prenylation and Geranylation of Oxindoles with Isoprene under Pd Catalysis
In nature, prenylation and geranylation are two important metabolic processes for the creation of hemiterpenoids and monoterpenoids under enzyme catalysis. Herein, we have demonstrated bioinspired unnatural prenylation and geranylation of oxindoles using the basic industrial feedstock isoprene throu...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2022-08, Vol.61 (32), p.e202207202-n/a |
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| creator | Zhao, Chao‐Yang Liu, Ying‐Ying Zhang, Xiang‐Xin He, Gu‐Cheng Liu, Heng Ji, Ding‐Wei Hu, Yan‐Cheng Chen, Qing‐An |
| description | In nature, prenylation and geranylation are two important metabolic processes for the creation of hemiterpenoids and monoterpenoids under enzyme catalysis. Herein, we have demonstrated bioinspired unnatural prenylation and geranylation of oxindoles using the basic industrial feedstock isoprene through ligand regulation under Pd catalysis. Pentenylated oxindoles (with C5 added) were attained with high selectivity when using a bisphosphine ligand, whereas upon switching to a monophosphine ligand, selectivity toward geranylated oxindoles (with C10 added) was achieved. Moreover, the head‐to‐head product could be further isomerized to an internal skipped diene under Pd−H catalysis. No stoichiometric by‐product was formed in the process.
A practical strategy has been developed for the bioinspired and ligand‐regulated chemoselective unnatural prenylation and geranylation of oxindoles with isoprene under Pd catalysis. The selectivity was governed by modulating the coordination geometry of the Pd catalyst. |
| doi_str_mv | 10.1002/anie.202207202 |
| format | Article |
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A practical strategy has been developed for the bioinspired and ligand‐regulated chemoselective unnatural prenylation and geranylation of oxindoles with isoprene under Pd catalysis. The selectivity was governed by modulating the coordination geometry of the Pd catalyst.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202207202</identifier><identifier>PMID: 35650687</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Catalysis ; Geranylation ; Isoprene ; Ligands ; Monoterpenoids ; Oxindoles ; Palladium ; Prenylation ; Selectivity</subject><ispartof>Angewandte Chemie International Edition, 2022-08, Vol.61 (32), p.e202207202-n/a</ispartof><rights>2022 Wiley‐VCH GmbH</rights><rights>2022 Wiley-VCH GmbH.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3732-e3c0b7340157ec177875d43b436d373c00695675491ceab0c0186385377d68cf3</citedby><cites>FETCH-LOGICAL-c3732-e3c0b7340157ec177875d43b436d373c00695675491ceab0c0186385377d68cf3</cites><orcidid>0000-0002-9129-2656</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.202207202$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202207202$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27903,27904,45553,45554</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/35650687$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Zhao, Chao‐Yang</creatorcontrib><creatorcontrib>Liu, Ying‐Ying</creatorcontrib><creatorcontrib>Zhang, Xiang‐Xin</creatorcontrib><creatorcontrib>He, Gu‐Cheng</creatorcontrib><creatorcontrib>Liu, Heng</creatorcontrib><creatorcontrib>Ji, Ding‐Wei</creatorcontrib><creatorcontrib>Hu, Yan‐Cheng</creatorcontrib><creatorcontrib>Chen, Qing‐An</creatorcontrib><title>Bioinspired and Ligand‐Regulated Unnatural Prenylation and Geranylation of Oxindoles with Isoprene under Pd Catalysis</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>In nature, prenylation and geranylation are two important metabolic processes for the creation of hemiterpenoids and monoterpenoids under enzyme catalysis. Herein, we have demonstrated bioinspired unnatural prenylation and geranylation of oxindoles using the basic industrial feedstock isoprene through ligand regulation under Pd catalysis. Pentenylated oxindoles (with C5 added) were attained with high selectivity when using a bisphosphine ligand, whereas upon switching to a monophosphine ligand, selectivity toward geranylated oxindoles (with C10 added) was achieved. Moreover, the head‐to‐head product could be further isomerized to an internal skipped diene under Pd−H catalysis. No stoichiometric by‐product was formed in the process.
A practical strategy has been developed for the bioinspired and ligand‐regulated chemoselective unnatural prenylation and geranylation of oxindoles with isoprene under Pd catalysis. The selectivity was governed by modulating the coordination geometry of the Pd catalyst.</description><subject>Catalysis</subject><subject>Geranylation</subject><subject>Isoprene</subject><subject>Ligands</subject><subject>Monoterpenoids</subject><subject>Oxindoles</subject><subject>Palladium</subject><subject>Prenylation</subject><subject>Selectivity</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNqFkc1uUzEQhS0EoqWwZYkssWFzg3-uf7IsUVsiRbRCdH3l2JPi6sYO9r0K2fUReEaehCkpQeqmm5nR0TdHozmEvOVswhkTH12KMBFMCGawPiPHXAneSGPkc5xbKRtjFT8ir2q9Rd5apl-SI6m0YtqaY7L9FHNMdRMLBOpSoIt4g-333a-vcDP2bkD5OiU3jMX19KpA2qEYc_oLX0BxByGv6OXPmELuodJtHL7Tec0b3AA6pgCFXgU6c4PrdzXW1-TFyvUV3jz0E3J9fvZt9rlZXF7MZ6eLxksjRQPSs6WRLePKgOfGWKNCK5et1AEBz5ieKm1UO-Ue3JJ5xq2WVuEDgrZ-JU_Ih73vpuQfI9ShW8fqoe9dgjzWTmgjDEMLiej7R-htHkvC65CaaosvZgKpyZ7yJddaYNVtSly7sus46-4j6e4j6Q6R4MK7B9txuYZwwP9lgMB0D2xjD7sn7LrTL_Oz_-Z_AKn2mIk</recordid><startdate>20220808</startdate><enddate>20220808</enddate><creator>Zhao, Chao‐Yang</creator><creator>Liu, Ying‐Ying</creator><creator>Zhang, Xiang‐Xin</creator><creator>He, Gu‐Cheng</creator><creator>Liu, Heng</creator><creator>Ji, Ding‐Wei</creator><creator>Hu, Yan‐Cheng</creator><creator>Chen, Qing‐An</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/0000-0002-9129-2656</orcidid></search><sort><creationdate>20220808</creationdate><title>Bioinspired and Ligand‐Regulated Unnatural Prenylation and Geranylation of Oxindoles with Isoprene under Pd Catalysis</title><author>Zhao, Chao‐Yang ; Liu, Ying‐Ying ; Zhang, Xiang‐Xin ; He, Gu‐Cheng ; Liu, Heng ; Ji, Ding‐Wei ; Hu, Yan‐Cheng ; Chen, Qing‐An</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3732-e3c0b7340157ec177875d43b436d373c00695675491ceab0c0186385377d68cf3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Catalysis</topic><topic>Geranylation</topic><topic>Isoprene</topic><topic>Ligands</topic><topic>Monoterpenoids</topic><topic>Oxindoles</topic><topic>Palladium</topic><topic>Prenylation</topic><topic>Selectivity</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zhao, Chao‐Yang</creatorcontrib><creatorcontrib>Liu, Ying‐Ying</creatorcontrib><creatorcontrib>Zhang, Xiang‐Xin</creatorcontrib><creatorcontrib>He, Gu‐Cheng</creatorcontrib><creatorcontrib>Liu, Heng</creatorcontrib><creatorcontrib>Ji, Ding‐Wei</creatorcontrib><creatorcontrib>Hu, Yan‐Cheng</creatorcontrib><creatorcontrib>Chen, Qing‐An</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>Zhao, Chao‐Yang</au><au>Liu, Ying‐Ying</au><au>Zhang, Xiang‐Xin</au><au>He, Gu‐Cheng</au><au>Liu, Heng</au><au>Ji, Ding‐Wei</au><au>Hu, Yan‐Cheng</au><au>Chen, Qing‐An</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Bioinspired and Ligand‐Regulated Unnatural Prenylation and Geranylation of Oxindoles with Isoprene under Pd Catalysis</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2022-08-08</date><risdate>2022</risdate><volume>61</volume><issue>32</issue><spage>e202207202</spage><epage>n/a</epage><pages>e202207202-n/a</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>In nature, prenylation and geranylation are two important metabolic processes for the creation of hemiterpenoids and monoterpenoids under enzyme catalysis. Herein, we have demonstrated bioinspired unnatural prenylation and geranylation of oxindoles using the basic industrial feedstock isoprene through ligand regulation under Pd catalysis. Pentenylated oxindoles (with C5 added) were attained with high selectivity when using a bisphosphine ligand, whereas upon switching to a monophosphine ligand, selectivity toward geranylated oxindoles (with C10 added) was achieved. Moreover, the head‐to‐head product could be further isomerized to an internal skipped diene under Pd−H catalysis. No stoichiometric by‐product was formed in the process.
A practical strategy has been developed for the bioinspired and ligand‐regulated chemoselective unnatural prenylation and geranylation of oxindoles with isoprene under Pd catalysis. The selectivity was governed by modulating the coordination geometry of the Pd catalyst.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>35650687</pmid><doi>10.1002/anie.202207202</doi><tpages>7</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-9129-2656</orcidid></addata></record> |
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| subjects | Catalysis Geranylation Isoprene Ligands Monoterpenoids Oxindoles Palladium Prenylation Selectivity |
| title | Bioinspired and Ligand‐Regulated Unnatural Prenylation and Geranylation of Oxindoles with Isoprene under Pd Catalysis |
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