Total Syntheses of Kopsaporine, Kopsinol and Kopsiloscine A
Kopsia alkaloids represent a complex class of natural products bearing a polycyclic ring system with two or three consecutive quaternary carbon centers. In this article, we report the first total synthesis of Kopsaporine related alkaloids. Features of our structure‐unit‐based strategy are an intramo...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2023-04, Vol.62 (15), p.e202218935-n/a |
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| creator | Tian, Hongchang Wu, Yinxia Li, Xiujuan Hao, Zhen He, Wenyan Huang, Xiangdi Chen, Wen Zhang, Hongbin |
| description | Kopsia alkaloids represent a complex class of natural products bearing a polycyclic ring system with two or three consecutive quaternary carbon centers. In this article, we report the first total synthesis of Kopsaporine related alkaloids. Features of our structure‐unit‐based strategy are an intramolecular Pummerer rearrangement induced nucleophilic cyclization/aza‐Prins cyclization to construct the highly functional hexahydrocarbazole skeleton, an olefin migration vinylogous alkylation to establish the C20 all‐carbon quaternary center, an iridium complex mediated radical addition to fuse the aspidofractine framework, an unprecedented IBX oxidation to introduce the α‐hydroxyketone moiety, and a bioinspired retro‐Aldol/Aldol reaction to convert kopsaporine to kopsiloscine A.
A unified strategy for the synthesis of Kopsia monoterpenoid indole alkaloids is described. Key transformations developed are an intramolecular Pummerer rearrangement induced nucleophilic cyclization/aza‐Prins cyclization to construct the highly functional hexahydrocarbazole skeleton, an iridium complex mediated radical addition to fuse the aspidofractine framework, and an IBX oxidation to introduce the α‐hydroxyketone moiety. |
| doi_str_mv | 10.1002/anie.202218935 |
| format | Article |
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A unified strategy for the synthesis of Kopsia monoterpenoid indole alkaloids is described. Key transformations developed are an intramolecular Pummerer rearrangement induced nucleophilic cyclization/aza‐Prins cyclization to construct the highly functional hexahydrocarbazole skeleton, an iridium complex mediated radical addition to fuse the aspidofractine framework, and an IBX oxidation to introduce the α‐hydroxyketone moiety.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202218935</identifier><identifier>PMID: 36759341</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Aldehydes ; Alkaloids ; Alkylation ; Carbon ; Cyclizations ; Iridium ; Iridium compounds ; Natural Products ; Oxidation ; Photochemistry ; Total Synthesis</subject><ispartof>Angewandte Chemie International Edition, 2023-04, Vol.62 (15), p.e202218935-n/a</ispartof><rights>2023 Wiley‐VCH GmbH</rights><rights>2023 Wiley-VCH GmbH.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3735-2453c0056f00c40f08ab9e456f59986dd814c1230ce25113d569b4f616c10eac3</citedby><cites>FETCH-LOGICAL-c3735-2453c0056f00c40f08ab9e456f59986dd814c1230ce25113d569b4f616c10eac3</cites><orcidid>0000-0002-2516-2634</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.202218935$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202218935$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/36759341$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Tian, Hongchang</creatorcontrib><creatorcontrib>Wu, Yinxia</creatorcontrib><creatorcontrib>Li, Xiujuan</creatorcontrib><creatorcontrib>Hao, Zhen</creatorcontrib><creatorcontrib>He, Wenyan</creatorcontrib><creatorcontrib>Huang, Xiangdi</creatorcontrib><creatorcontrib>Chen, Wen</creatorcontrib><creatorcontrib>Zhang, Hongbin</creatorcontrib><title>Total Syntheses of Kopsaporine, Kopsinol and Kopsiloscine A</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>Kopsia alkaloids represent a complex class of natural products bearing a polycyclic ring system with two or three consecutive quaternary carbon centers. In this article, we report the first total synthesis of Kopsaporine related alkaloids. Features of our structure‐unit‐based strategy are an intramolecular Pummerer rearrangement induced nucleophilic cyclization/aza‐Prins cyclization to construct the highly functional hexahydrocarbazole skeleton, an olefin migration vinylogous alkylation to establish the C20 all‐carbon quaternary center, an iridium complex mediated radical addition to fuse the aspidofractine framework, an unprecedented IBX oxidation to introduce the α‐hydroxyketone moiety, and a bioinspired retro‐Aldol/Aldol reaction to convert kopsaporine to kopsiloscine A.
A unified strategy for the synthesis of Kopsia monoterpenoid indole alkaloids is described. Key transformations developed are an intramolecular Pummerer rearrangement induced nucleophilic cyclization/aza‐Prins cyclization to construct the highly functional hexahydrocarbazole skeleton, an iridium complex mediated radical addition to fuse the aspidofractine framework, and an IBX oxidation to introduce the α‐hydroxyketone moiety.</description><subject>Aldehydes</subject><subject>Alkaloids</subject><subject>Alkylation</subject><subject>Carbon</subject><subject>Cyclizations</subject><subject>Iridium</subject><subject>Iridium compounds</subject><subject>Natural Products</subject><subject>Oxidation</subject><subject>Photochemistry</subject><subject>Total Synthesis</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNqFkL1OwzAURi0EoqWwMqJILAykXP8nA0NVFaioYKDMlus4IlUal7gR6sbCi_IkuKQUiYXp-pPPPbr6EDrF0McA5EpXhe0TIAQnKeV7qIs5wTGVku6HN6M0lgnHHXTk_TzwSQLiEHWokDylDHfR9dStdBk9ravVi_XWRy6P7t3S66Wri8pefoeicmWkq6wNpfMmfH2-fwyO0UGuS29PtrOHnm9G0-FdPHm8HQ8Hk9hQSXlMGKcGgIscwDDIIdGz1LKQeZomIssSzAwmFIwlHGOacZHOWC6wMBisNrSHLlrvsnavjfUrtSi8sWWpK-sar4iUXBAGMgno-R907pq6CtcFKsUgBQANVL-lTO28r22ulnWx0PVaYVCbYtWmWLUrNiycbbXNbGGzHf7TZADSFngrSrv-R6cGD-PRr_wLoeWDCw</recordid><startdate>20230403</startdate><enddate>20230403</enddate><creator>Tian, Hongchang</creator><creator>Wu, Yinxia</creator><creator>Li, Xiujuan</creator><creator>Hao, Zhen</creator><creator>He, Wenyan</creator><creator>Huang, Xiangdi</creator><creator>Chen, Wen</creator><creator>Zhang, Hongbin</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/0000-0002-2516-2634</orcidid></search><sort><creationdate>20230403</creationdate><title>Total Syntheses of Kopsaporine, Kopsinol and Kopsiloscine A</title><author>Tian, Hongchang ; Wu, Yinxia ; Li, Xiujuan ; Hao, Zhen ; He, Wenyan ; Huang, Xiangdi ; Chen, Wen ; Zhang, Hongbin</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3735-2453c0056f00c40f08ab9e456f59986dd814c1230ce25113d569b4f616c10eac3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Aldehydes</topic><topic>Alkaloids</topic><topic>Alkylation</topic><topic>Carbon</topic><topic>Cyclizations</topic><topic>Iridium</topic><topic>Iridium compounds</topic><topic>Natural Products</topic><topic>Oxidation</topic><topic>Photochemistry</topic><topic>Total Synthesis</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tian, Hongchang</creatorcontrib><creatorcontrib>Wu, Yinxia</creatorcontrib><creatorcontrib>Li, Xiujuan</creatorcontrib><creatorcontrib>Hao, Zhen</creatorcontrib><creatorcontrib>He, Wenyan</creatorcontrib><creatorcontrib>Huang, Xiangdi</creatorcontrib><creatorcontrib>Chen, Wen</creatorcontrib><creatorcontrib>Zhang, Hongbin</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>Tian, Hongchang</au><au>Wu, Yinxia</au><au>Li, Xiujuan</au><au>Hao, Zhen</au><au>He, Wenyan</au><au>Huang, Xiangdi</au><au>Chen, Wen</au><au>Zhang, Hongbin</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Total Syntheses of Kopsaporine, Kopsinol and Kopsiloscine A</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2023-04-03</date><risdate>2023</risdate><volume>62</volume><issue>15</issue><spage>e202218935</spage><epage>n/a</epage><pages>e202218935-n/a</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>Kopsia alkaloids represent a complex class of natural products bearing a polycyclic ring system with two or three consecutive quaternary carbon centers. In this article, we report the first total synthesis of Kopsaporine related alkaloids. Features of our structure‐unit‐based strategy are an intramolecular Pummerer rearrangement induced nucleophilic cyclization/aza‐Prins cyclization to construct the highly functional hexahydrocarbazole skeleton, an olefin migration vinylogous alkylation to establish the C20 all‐carbon quaternary center, an iridium complex mediated radical addition to fuse the aspidofractine framework, an unprecedented IBX oxidation to introduce the α‐hydroxyketone moiety, and a bioinspired retro‐Aldol/Aldol reaction to convert kopsaporine to kopsiloscine A.
A unified strategy for the synthesis of Kopsia monoterpenoid indole alkaloids is described. Key transformations developed are an intramolecular Pummerer rearrangement induced nucleophilic cyclization/aza‐Prins cyclization to construct the highly functional hexahydrocarbazole skeleton, an iridium complex mediated radical addition to fuse the aspidofractine framework, and an IBX oxidation to introduce the α‐hydroxyketone moiety.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>36759341</pmid><doi>10.1002/anie.202218935</doi><tpages>6</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-2516-2634</orcidid></addata></record> |
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| subjects | Aldehydes Alkaloids Alkylation Carbon Cyclizations Iridium Iridium compounds Natural Products Oxidation Photochemistry Total Synthesis |
| title | Total Syntheses of Kopsaporine, Kopsinol and Kopsiloscine A |
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