Cobalt-Catalyzed Oxidase C−H/N−H Alkyne Annulation: Mechanistic Insights and Access to Anticancer Agents
Cp*‐free cobalt‐catalyzed alkyne annulations by C−H/N−H functionalizations were accomplished with molecular O2 as the sole oxidant. The user‐friendly oxidase strategy proved viable with various internal and terminal alkynes through kinetically relevant C−H cobaltation, providing among others step‐ec...
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| Veröffentlicht in: | Chemistry : a European journal 2016-05, Vol.22 (20), p.6759-6763 |
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| creator | Mei, Ruhuai Wang, Hui Warratz, Svenja Macgregor, Stuart A. Ackermann, Lutz |
| description | Cp*‐free cobalt‐catalyzed alkyne annulations by C−H/N−H functionalizations were accomplished with molecular O2 as the sole oxidant. The user‐friendly oxidase strategy proved viable with various internal and terminal alkynes through kinetically relevant C−H cobaltation, providing among others step‐economical access to the anticancer topoisomerase‐I inhibitor 21,22‐dimethoxyrosettacin. DFT calculations suggest that electronic effects control the regioselectivity of the alkyne insertion step.
Mit O2: Co(OAc)2 enabled the aerobic C−H/N−H functionalization with O2 as the sole oxidant under Cp*‐free conditions, which enabled step‐economical access to anticancer isoquinolones by highly selective C−H activation (see scheme, Cp*=pentamethylcyclopentadienyl). |
| doi_str_mv | 10.1002/chem.201601101 |
| format | Article |
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Mit O2: Co(OAc)2 enabled the aerobic C−H/N−H functionalization with O2 as the sole oxidant under Cp*‐free conditions, which enabled step‐economical access to anticancer isoquinolones by highly selective C−H activation (see scheme, Cp*=pentamethylcyclopentadienyl).</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.201601101</identifier><identifier>PMID: 26992149</identifier><identifier>CODEN: CEUJED</identifier><language>eng</language><publisher>Germany: Blackwell Publishing Ltd</publisher><subject>Alkynes ; Alkynes - chemistry ; annulation ; Anticancer properties ; Antineoplastic Agents - chemical synthesis ; Antineoplastic Agents - chemistry ; Antitumor agents ; Cancer ; Catalysis ; Chemical reactions ; Chemistry ; Cobalt ; Coordination Complexes - chemistry ; C−H activation ; density functional calculations ; Economics ; Electronic properties ; Heterocyclic Compounds, 4 or More Rings - chemical synthesis ; Heterocyclic Compounds, 4 or More Rings - chemistry ; Inhibitors ; Insertion ; Isoquinolines - chemical synthesis ; Isoquinolines - chemistry ; isoquinolones ; Mathematical analysis ; Organic chemistry ; Oxidants ; Oxidase ; Oxidizing agents ; Oxidoreductases - chemistry ; Quantum Theory ; Regioselectivity ; Sole ; Stereoisomerism ; Terminals ; Thermodynamics ; Topoisomerase I Inhibitors - chemical synthesis ; Topoisomerase I Inhibitors - chemistry</subject><ispartof>Chemistry : a European journal, 2016-05, Vol.22 (20), p.6759-6763</ispartof><rights>2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c6781-6b233fc30cb92e31bd0e29c92be54c850e2ed144dede0fc97d2f4a6d73b6ebc33</citedby><cites>FETCH-LOGICAL-c6781-6b233fc30cb92e31bd0e29c92be54c850e2ed144dede0fc97d2f4a6d73b6ebc33</cites><orcidid>0000-0003-3454-6776 ; 0000-0001-7034-8772</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%2Fchem.201601101$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.201601101$$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/26992149$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Mei, Ruhuai</creatorcontrib><creatorcontrib>Wang, Hui</creatorcontrib><creatorcontrib>Warratz, Svenja</creatorcontrib><creatorcontrib>Macgregor, Stuart A.</creatorcontrib><creatorcontrib>Ackermann, Lutz</creatorcontrib><title>Cobalt-Catalyzed Oxidase C−H/N−H Alkyne Annulation: Mechanistic Insights and Access to Anticancer Agents</title><title>Chemistry : a European journal</title><addtitle>Chem. Eur. J</addtitle><description>Cp*‐free cobalt‐catalyzed alkyne annulations by C−H/N−H functionalizations were accomplished with molecular O2 as the sole oxidant. The user‐friendly oxidase strategy proved viable with various internal and terminal alkynes through kinetically relevant C−H cobaltation, providing among others step‐economical access to the anticancer topoisomerase‐I inhibitor 21,22‐dimethoxyrosettacin. DFT calculations suggest that electronic effects control the regioselectivity of the alkyne insertion step.
Mit O2: Co(OAc)2 enabled the aerobic C−H/N−H functionalization with O2 as the sole oxidant under Cp*‐free conditions, which enabled step‐economical access to anticancer isoquinolones by highly selective C−H activation (see scheme, Cp*=pentamethylcyclopentadienyl).</description><subject>Alkynes</subject><subject>Alkynes - chemistry</subject><subject>annulation</subject><subject>Anticancer properties</subject><subject>Antineoplastic Agents - chemical synthesis</subject><subject>Antineoplastic Agents - chemistry</subject><subject>Antitumor agents</subject><subject>Cancer</subject><subject>Catalysis</subject><subject>Chemical reactions</subject><subject>Chemistry</subject><subject>Cobalt</subject><subject>Coordination Complexes - chemistry</subject><subject>C−H activation</subject><subject>density functional calculations</subject><subject>Economics</subject><subject>Electronic properties</subject><subject>Heterocyclic Compounds, 4 or More Rings - chemical synthesis</subject><subject>Heterocyclic Compounds, 4 or More Rings - chemistry</subject><subject>Inhibitors</subject><subject>Insertion</subject><subject>Isoquinolines - chemical synthesis</subject><subject>Isoquinolines - chemistry</subject><subject>isoquinolones</subject><subject>Mathematical analysis</subject><subject>Organic chemistry</subject><subject>Oxidants</subject><subject>Oxidase</subject><subject>Oxidizing agents</subject><subject>Oxidoreductases - chemistry</subject><subject>Quantum Theory</subject><subject>Regioselectivity</subject><subject>Sole</subject><subject>Stereoisomerism</subject><subject>Terminals</subject><subject>Thermodynamics</subject><subject>Topoisomerase I Inhibitors - chemical synthesis</subject><subject>Topoisomerase I Inhibitors - chemistry</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqNks9u1DAQxiMEotvClSOKxIVLtuP_Mbc0tN1K2_ZSQOJiOfZsN23WKXEiujwBZx6RJyGrLSvEgXLxyPLv-8aj-ZLkFYEpAaCHbomrKQUigRAgT5IJEZRkTEnxNJmA5iqTgum9ZD_GGwDQkrHnyR6VWlPC9SRpyrayTZ-VtrfN-hv69PK-9jZiWv78_mN2eLE506K5XQdMixCGxvZ1G96l5-iWNtSxr116FmJ9vexjaoNPC-cwxrRvR3x8tMFhlxbXGPr4Inm2sE3Elw_1IPlwcnxVzrL55elZWcwzJ1VOMllRxhaOgas0RUYqD0i107RCwV0uxht6wrlHj7BwWnm64FZ6xSqJlWPsIHm79b3r2i8Dxt6s6uiwaWzAdoiG5ERozYCr_0BBCJBK6cdRlSvIBWebD7z5C71phy6MMxuiQQmR58D_SalcUs7G7iM13VKua2PscGHuunplu7UhYDYZMJsMmF0GRsHrB9uhWqHf4b-XPgJ6C3ytG1w_YmfK2fH5n-bZVjtuHu93WtvdGqmYEubTxak5IvRq_vH9ZwPsFzQozDs</recordid><startdate>20160510</startdate><enddate>20160510</enddate><creator>Mei, Ruhuai</creator><creator>Wang, Hui</creator><creator>Warratz, Svenja</creator><creator>Macgregor, Stuart A.</creator><creator>Ackermann, Lutz</creator><general>Blackwell Publishing Ltd</general><general>Wiley Subscription Services, Inc</general><scope>BSCLL</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>K9.</scope><scope>7X8</scope><scope>7QO</scope><scope>FR3</scope><scope>P64</scope><orcidid>https://orcid.org/0000-0003-3454-6776</orcidid><orcidid>https://orcid.org/0000-0001-7034-8772</orcidid></search><sort><creationdate>20160510</creationdate><title>Cobalt-Catalyzed Oxidase C−H/N−H Alkyne Annulation: Mechanistic Insights and Access to Anticancer Agents</title><author>Mei, Ruhuai ; Wang, Hui ; Warratz, Svenja ; Macgregor, Stuart A. ; Ackermann, Lutz</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c6781-6b233fc30cb92e31bd0e29c92be54c850e2ed144dede0fc97d2f4a6d73b6ebc33</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Alkynes</topic><topic>Alkynes - chemistry</topic><topic>annulation</topic><topic>Anticancer properties</topic><topic>Antineoplastic Agents - chemical synthesis</topic><topic>Antineoplastic Agents - chemistry</topic><topic>Antitumor agents</topic><topic>Cancer</topic><topic>Catalysis</topic><topic>Chemical reactions</topic><topic>Chemistry</topic><topic>Cobalt</topic><topic>Coordination Complexes - chemistry</topic><topic>C−H activation</topic><topic>density functional calculations</topic><topic>Economics</topic><topic>Electronic properties</topic><topic>Heterocyclic Compounds, 4 or More Rings - chemical synthesis</topic><topic>Heterocyclic Compounds, 4 or More Rings - chemistry</topic><topic>Inhibitors</topic><topic>Insertion</topic><topic>Isoquinolines - chemical synthesis</topic><topic>Isoquinolines - chemistry</topic><topic>isoquinolones</topic><topic>Mathematical analysis</topic><topic>Organic chemistry</topic><topic>Oxidants</topic><topic>Oxidase</topic><topic>Oxidizing agents</topic><topic>Oxidoreductases - chemistry</topic><topic>Quantum Theory</topic><topic>Regioselectivity</topic><topic>Sole</topic><topic>Stereoisomerism</topic><topic>Terminals</topic><topic>Thermodynamics</topic><topic>Topoisomerase I Inhibitors - chemical synthesis</topic><topic>Topoisomerase I Inhibitors - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mei, Ruhuai</creatorcontrib><creatorcontrib>Wang, Hui</creatorcontrib><creatorcontrib>Warratz, Svenja</creatorcontrib><creatorcontrib>Macgregor, Stuart A.</creatorcontrib><creatorcontrib>Ackermann, Lutz</creatorcontrib><collection>Istex</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><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>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>Biotechnology Research Abstracts</collection><collection>Engineering Research Database</collection><collection>Biotechnology and BioEngineering Abstracts</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mei, Ruhuai</au><au>Wang, Hui</au><au>Warratz, Svenja</au><au>Macgregor, Stuart A.</au><au>Ackermann, Lutz</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Cobalt-Catalyzed Oxidase C−H/N−H Alkyne Annulation: Mechanistic Insights and Access to Anticancer Agents</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chem. Eur. J</addtitle><date>2016-05-10</date><risdate>2016</risdate><volume>22</volume><issue>20</issue><spage>6759</spage><epage>6763</epage><pages>6759-6763</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><coden>CEUJED</coden><abstract>Cp*‐free cobalt‐catalyzed alkyne annulations by C−H/N−H functionalizations were accomplished with molecular O2 as the sole oxidant. The user‐friendly oxidase strategy proved viable with various internal and terminal alkynes through kinetically relevant C−H cobaltation, providing among others step‐economical access to the anticancer topoisomerase‐I inhibitor 21,22‐dimethoxyrosettacin. DFT calculations suggest that electronic effects control the regioselectivity of the alkyne insertion step.
Mit O2: Co(OAc)2 enabled the aerobic C−H/N−H functionalization with O2 as the sole oxidant under Cp*‐free conditions, which enabled step‐economical access to anticancer isoquinolones by highly selective C−H activation (see scheme, Cp*=pentamethylcyclopentadienyl).</abstract><cop>Germany</cop><pub>Blackwell Publishing Ltd</pub><pmid>26992149</pmid><doi>10.1002/chem.201601101</doi><tpages>5</tpages><orcidid>https://orcid.org/0000-0003-3454-6776</orcidid><orcidid>https://orcid.org/0000-0001-7034-8772</orcidid></addata></record> |
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| subjects | Alkynes Alkynes - chemistry annulation Anticancer properties Antineoplastic Agents - chemical synthesis Antineoplastic Agents - chemistry Antitumor agents Cancer Catalysis Chemical reactions Chemistry Cobalt Coordination Complexes - chemistry C−H activation density functional calculations Economics Electronic properties Heterocyclic Compounds, 4 or More Rings - chemical synthesis Heterocyclic Compounds, 4 or More Rings - chemistry Inhibitors Insertion Isoquinolines - chemical synthesis Isoquinolines - chemistry isoquinolones Mathematical analysis Organic chemistry Oxidants Oxidase Oxidizing agents Oxidoreductases - chemistry Quantum Theory Regioselectivity Sole Stereoisomerism Terminals Thermodynamics Topoisomerase I Inhibitors - chemical synthesis Topoisomerase I Inhibitors - chemistry |
| title | Cobalt-Catalyzed Oxidase C−H/N−H Alkyne Annulation: Mechanistic Insights and Access to Anticancer Agents |
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