An Asymmetric Pathway to Dendrobine by a Transition‐Metal‐Catalyzed Cascade Process
An asymmetric pathway to the caged tetracyclic pyrrolidine alkaloid, dendrobine, is reported. The successful synthetic strategy features a one‐pot, sequential palladium‐catalyzed enyne cycloisomerization and rhodium‐catalyzed diene‐assisted pyrrolidine formation by allylic CH activation. The develop...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2017-09, Vol.56 (40), p.12250-12254 |
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| creator | Lee, Yujin Rochette, Elise M. Kim, Junyong Chen, David Y.‐K. |
| description | An asymmetric pathway to the caged tetracyclic pyrrolidine alkaloid, dendrobine, is reported. The successful synthetic strategy features a one‐pot, sequential palladium‐catalyzed enyne cycloisomerization and rhodium‐catalyzed diene‐assisted pyrrolidine formation by allylic CH activation. The developed transition‐metal‐catalyzed cascade process permits rapid access to the dendrobine core structure and circumvents the handling of labile intermediates. An intramolecular aldol condensation under carefully defined reaction conditions takes place with a concomitant detosylation, followed by reductive amine methylation, to afford a late‐stage intermediate (previously identified by several prior dendrobine syntheses) in only 10 synthetic steps overall.
An asymmetric pathway to polycyclic alkaloid dendrobine was developed comprising a one‐pot palladium‐catalyzed enyne cycloisomerization, and rhodium‐catalyzed diene‐assisted pyrrolidine formation by allylic CH activation. Intramolecular aldol condensation with concomitant detosylation, followed by reductive amination, afforded an advanced intermediate in only 10 synthetic steps. |
| doi_str_mv | 10.1002/anie.201705713 |
| format | Article |
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An asymmetric pathway to polycyclic alkaloid dendrobine was developed comprising a one‐pot palladium‐catalyzed enyne cycloisomerization, and rhodium‐catalyzed diene‐assisted pyrrolidine formation by allylic CH activation. Intramolecular aldol condensation with concomitant detosylation, followed by reductive amination, afforded an advanced intermediate in only 10 synthetic steps.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201705713</identifier><identifier>PMID: 28836368</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Aldehydes ; alkaloids ; cascade reactions ; Catalysis ; homogeneous catalysis ; Intermediates ; Isomerization ; Metals ; Methylation ; Palladium ; Pyrrolidine ; Rhodium ; total synthesis ; transition metals</subject><ispartof>Angewandte Chemie International Edition, 2017-09, Vol.56 (40), p.12250-12254</ispartof><rights>2017 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4103-abc09560a759d7fa18a9ef89da9fba176e89ca2a0add123d2d04a58488265c123</citedby><cites>FETCH-LOGICAL-c4103-abc09560a759d7fa18a9ef89da9fba176e89ca2a0add123d2d04a58488265c123</cites></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.201705713$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201705713$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1416,27923,27924,45573,45574</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/28836368$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Lee, Yujin</creatorcontrib><creatorcontrib>Rochette, Elise M.</creatorcontrib><creatorcontrib>Kim, Junyong</creatorcontrib><creatorcontrib>Chen, David Y.‐K.</creatorcontrib><title>An Asymmetric Pathway to Dendrobine by a Transition‐Metal‐Catalyzed Cascade Process</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>An asymmetric pathway to the caged tetracyclic pyrrolidine alkaloid, dendrobine, is reported. The successful synthetic strategy features a one‐pot, sequential palladium‐catalyzed enyne cycloisomerization and rhodium‐catalyzed diene‐assisted pyrrolidine formation by allylic CH activation. The developed transition‐metal‐catalyzed cascade process permits rapid access to the dendrobine core structure and circumvents the handling of labile intermediates. An intramolecular aldol condensation under carefully defined reaction conditions takes place with a concomitant detosylation, followed by reductive amine methylation, to afford a late‐stage intermediate (previously identified by several prior dendrobine syntheses) in only 10 synthetic steps overall.
An asymmetric pathway to polycyclic alkaloid dendrobine was developed comprising a one‐pot palladium‐catalyzed enyne cycloisomerization, and rhodium‐catalyzed diene‐assisted pyrrolidine formation by allylic CH activation. Intramolecular aldol condensation with concomitant detosylation, followed by reductive amination, afforded an advanced intermediate in only 10 synthetic steps.</description><subject>Aldehydes</subject><subject>alkaloids</subject><subject>cascade reactions</subject><subject>Catalysis</subject><subject>homogeneous catalysis</subject><subject>Intermediates</subject><subject>Isomerization</subject><subject>Metals</subject><subject>Methylation</subject><subject>Palladium</subject><subject>Pyrrolidine</subject><subject>Rhodium</subject><subject>total synthesis</subject><subject>transition metals</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNqF0Mtq3DAYBWARGjLJpNsui6CbbjzRxZKl5TDNDaZtFhO6NL-l39TBl1TyEJxVHiHPmCeJwiQpdNPVEeLTQRxCPnG24IyJE-gbXAjGC6YKLvfIIVeCZ7Io5Id0zqXMCqP4jBzFeJO8MUwfkFlKqaU2h-TXsqfLOHUdjqFx9ArG33cw0XGg37D3YaiaHmk1UaCbAH1sxmbonx4ev-MIbcoVpJzu0dMVRAce6VUYHMZ4TPZraCN-fM05uT473awusvXP88vVcp25nDOZQeWYVZpBoawvauAGLNbGerB1BbzQaKwDAQy850J64VkOyuTGCK1cupmTr7ve2zD82WIcy66JDtsWehy2seRWCq6FtirRL__Qm2Eb-vS7pHKW50JxndRip1wYYgxYl7eh6SBMJWfly-Tly-Tl--TpwefX2m3VoX_nbxsnYHfgrmlx-k9dufxxefq3_BmXA46W</recordid><startdate>20170925</startdate><enddate>20170925</enddate><creator>Lee, Yujin</creator><creator>Rochette, Elise M.</creator><creator>Kim, Junyong</creator><creator>Chen, David Y.‐K.</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></search><sort><creationdate>20170925</creationdate><title>An Asymmetric Pathway to Dendrobine by a Transition‐Metal‐Catalyzed Cascade Process</title><author>Lee, Yujin ; Rochette, Elise M. ; Kim, Junyong ; Chen, David Y.‐K.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4103-abc09560a759d7fa18a9ef89da9fba176e89ca2a0add123d2d04a58488265c123</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><topic>Aldehydes</topic><topic>alkaloids</topic><topic>cascade reactions</topic><topic>Catalysis</topic><topic>homogeneous catalysis</topic><topic>Intermediates</topic><topic>Isomerization</topic><topic>Metals</topic><topic>Methylation</topic><topic>Palladium</topic><topic>Pyrrolidine</topic><topic>Rhodium</topic><topic>total synthesis</topic><topic>transition metals</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Lee, Yujin</creatorcontrib><creatorcontrib>Rochette, Elise M.</creatorcontrib><creatorcontrib>Kim, Junyong</creatorcontrib><creatorcontrib>Chen, David Y.‐K.</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>Lee, Yujin</au><au>Rochette, Elise M.</au><au>Kim, Junyong</au><au>Chen, David Y.‐K.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>An Asymmetric Pathway to Dendrobine by a Transition‐Metal‐Catalyzed Cascade Process</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2017-09-25</date><risdate>2017</risdate><volume>56</volume><issue>40</issue><spage>12250</spage><epage>12254</epage><pages>12250-12254</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>An asymmetric pathway to the caged tetracyclic pyrrolidine alkaloid, dendrobine, is reported. The successful synthetic strategy features a one‐pot, sequential palladium‐catalyzed enyne cycloisomerization and rhodium‐catalyzed diene‐assisted pyrrolidine formation by allylic CH activation. The developed transition‐metal‐catalyzed cascade process permits rapid access to the dendrobine core structure and circumvents the handling of labile intermediates. An intramolecular aldol condensation under carefully defined reaction conditions takes place with a concomitant detosylation, followed by reductive amine methylation, to afford a late‐stage intermediate (previously identified by several prior dendrobine syntheses) in only 10 synthetic steps overall.
An asymmetric pathway to polycyclic alkaloid dendrobine was developed comprising a one‐pot palladium‐catalyzed enyne cycloisomerization, and rhodium‐catalyzed diene‐assisted pyrrolidine formation by allylic CH activation. Intramolecular aldol condensation with concomitant detosylation, followed by reductive amination, afforded an advanced intermediate in only 10 synthetic steps.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>28836368</pmid><doi>10.1002/anie.201705713</doi><tpages>5</tpages><edition>International ed. in English</edition></addata></record> |
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| subjects | Aldehydes alkaloids cascade reactions Catalysis homogeneous catalysis Intermediates Isomerization Metals Methylation Palladium Pyrrolidine Rhodium total synthesis transition metals |
| title | An Asymmetric Pathway to Dendrobine by a Transition‐Metal‐Catalyzed Cascade Process |
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