Redox‐Neutral Coupling between Two C(sp3)−H Bonds Enabled by 1,4‐Palladium Shift for the Synthesis of Fused Heterocycles
The intramolecular coupling of two C(sp3)−H bonds to forge a C(sp3)−C(sp3) bond is enabled by 1,4‐Pd shift from a trisubstituted aryl bromide. Contrary to most C(sp3)−C(sp3) cross‐dehydrogenative couplings, this reaction operates under redox‐neutral conditions, with the C−Br bond acting as an intern...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2019-10, Vol.58 (41), p.14625-14628 |
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| creator | Rocaboy, Ronan Anastasiou, Ioannis Baudoin, Olivier |
| description | The intramolecular coupling of two C(sp3)−H bonds to forge a C(sp3)−C(sp3) bond is enabled by 1,4‐Pd shift from a trisubstituted aryl bromide. Contrary to most C(sp3)−C(sp3) cross‐dehydrogenative couplings, this reaction operates under redox‐neutral conditions, with the C−Br bond acting as an internal oxidant. Furthermore, it allows the coupling between two moderately acidic primary or secondary C−H bonds, which are adjacent to an oxygen or nitrogen atom on one side, and benzylic or adjacent to a carbonyl group on the other side. A variety of valuable fused heterocycles were obtained from easily accessible ortho‐bromophenol and aniline precursors. The second C−H bond cleavage was successfully replaced with carbonyl insertion to generate other types of C(sp3)‐C(sp3) bonds.
A variety of fused heterocycles are obtained from easily accessible ortho‐bromophenol and aniline precursors by intramolecular coupling of two C(sp3)−H bonds, enabled by 1,4‐Pd shift from a trisubstituted aryl bromide. Unlike most C(sp3)−C(sp3) cross‐dehydrogenative couplings, this reaction operates under redox‐neutral conditions, with the C−Br bond acting as an internal oxidant. |
| doi_str_mv | 10.1002/anie.201908460 |
| format | Article |
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A variety of fused heterocycles are obtained from easily accessible ortho‐bromophenol and aniline precursors by intramolecular coupling of two C(sp3)−H bonds, enabled by 1,4‐Pd shift from a trisubstituted aryl bromide. Unlike most C(sp3)−C(sp3) cross‐dehydrogenative couplings, this reaction operates under redox‐neutral conditions, with the C−Br bond acting as an internal oxidant.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201908460</identifier><identifier>PMID: 31397959</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Acidic oxides ; Aniline ; Aromatic compounds ; Bonding ; Carbonyl compounds ; Carbonyl groups ; Carbonyls ; Couplings ; C−H activation ; Dehydrogenation ; domino reactions ; heterocycles ; Hydrogen bonds ; Palladium</subject><ispartof>Angewandte Chemie International Edition, 2019-10, Vol.58 (41), p.14625-14628</ispartof><rights>2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5160-b1899b28e731f6840870c34e5fd895900f734d97de6ae3fc9570e4a996632eb3</citedby><cites>FETCH-LOGICAL-c5160-b1899b28e731f6840870c34e5fd895900f734d97de6ae3fc9570e4a996632eb3</cites><orcidid>0000-0002-0847-8493</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.201908460$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201908460$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/31397959$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Rocaboy, Ronan</creatorcontrib><creatorcontrib>Anastasiou, Ioannis</creatorcontrib><creatorcontrib>Baudoin, Olivier</creatorcontrib><title>Redox‐Neutral Coupling between Two C(sp3)−H Bonds Enabled by 1,4‐Palladium Shift for the Synthesis of Fused Heterocycles</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>The intramolecular coupling of two C(sp3)−H bonds to forge a C(sp3)−C(sp3) bond is enabled by 1,4‐Pd shift from a trisubstituted aryl bromide. Contrary to most C(sp3)−C(sp3) cross‐dehydrogenative couplings, this reaction operates under redox‐neutral conditions, with the C−Br bond acting as an internal oxidant. Furthermore, it allows the coupling between two moderately acidic primary or secondary C−H bonds, which are adjacent to an oxygen or nitrogen atom on one side, and benzylic or adjacent to a carbonyl group on the other side. A variety of valuable fused heterocycles were obtained from easily accessible ortho‐bromophenol and aniline precursors. The second C−H bond cleavage was successfully replaced with carbonyl insertion to generate other types of C(sp3)‐C(sp3) bonds.
A variety of fused heterocycles are obtained from easily accessible ortho‐bromophenol and aniline precursors by intramolecular coupling of two C(sp3)−H bonds, enabled by 1,4‐Pd shift from a trisubstituted aryl bromide. Unlike most C(sp3)−C(sp3) cross‐dehydrogenative couplings, this reaction operates under redox‐neutral conditions, with the C−Br bond acting as an internal oxidant.</description><subject>Acidic oxides</subject><subject>Aniline</subject><subject>Aromatic compounds</subject><subject>Bonding</subject><subject>Carbonyl compounds</subject><subject>Carbonyl groups</subject><subject>Carbonyls</subject><subject>Couplings</subject><subject>C−H activation</subject><subject>Dehydrogenation</subject><subject>domino reactions</subject><subject>heterocycles</subject><subject>Hydrogen bonds</subject><subject>Palladium</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNqFkTtP7DAQhS0E4t1SXlm6DUhk8SOJ7XJZLSwSAgTbR04yvgRl48VOtKRBlJSIn8gvwWh5SLehmim-c3RmDkJ7lAwoIexINxUMGKGKyDglK2iTJoxGXAi-GvaY80jIhG6gLe_vAi8lSdfRBqdcCZWoTfR4DaV9eHt6uYCudbrGI9vN66r5h3NoFwANni4sHu37OT94e36d4GPblB6PG53XUOK8x_QwDvIrXde6rLoZvrmtTIuNdbi9BXzTN2H4ymNr8Enng2YCLThb9EUNfgetGV172P2c22h6Mp6OJtH55enZaHgeFQlNSZRTqVTOJAhOTSpjIgUpeAyJKWU4gxAjeFwqUUKqgZtCJYJArJVKU84g59tof2k7d_a-A99ms8oXECI3YDufMSaoTFj4YUD__ofe2c41IVyglJCCqVgFarCkCme9d2Cyuatm2vUZJdlHMdlHMdl3MUHw59O2y2dQfuNfTQRALYFFVUP_i102vDgb_5i_Ax1Am1Y</recordid><startdate>20191007</startdate><enddate>20191007</enddate><creator>Rocaboy, Ronan</creator><creator>Anastasiou, Ioannis</creator><creator>Baudoin, Olivier</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/0000-0002-0847-8493</orcidid></search><sort><creationdate>20191007</creationdate><title>Redox‐Neutral Coupling between Two C(sp3)−H Bonds Enabled by 1,4‐Palladium Shift for the Synthesis of Fused Heterocycles</title><author>Rocaboy, Ronan ; Anastasiou, Ioannis ; Baudoin, Olivier</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5160-b1899b28e731f6840870c34e5fd895900f734d97de6ae3fc9570e4a996632eb3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Acidic oxides</topic><topic>Aniline</topic><topic>Aromatic compounds</topic><topic>Bonding</topic><topic>Carbonyl compounds</topic><topic>Carbonyl groups</topic><topic>Carbonyls</topic><topic>Couplings</topic><topic>C−H activation</topic><topic>Dehydrogenation</topic><topic>domino reactions</topic><topic>heterocycles</topic><topic>Hydrogen bonds</topic><topic>Palladium</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Rocaboy, Ronan</creatorcontrib><creatorcontrib>Anastasiou, Ioannis</creatorcontrib><creatorcontrib>Baudoin, Olivier</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>Rocaboy, Ronan</au><au>Anastasiou, Ioannis</au><au>Baudoin, Olivier</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Redox‐Neutral Coupling between Two C(sp3)−H Bonds Enabled by 1,4‐Palladium Shift for the Synthesis of Fused Heterocycles</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2019-10-07</date><risdate>2019</risdate><volume>58</volume><issue>41</issue><spage>14625</spage><epage>14628</epage><pages>14625-14628</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>The intramolecular coupling of two C(sp3)−H bonds to forge a C(sp3)−C(sp3) bond is enabled by 1,4‐Pd shift from a trisubstituted aryl bromide. Contrary to most C(sp3)−C(sp3) cross‐dehydrogenative couplings, this reaction operates under redox‐neutral conditions, with the C−Br bond acting as an internal oxidant. Furthermore, it allows the coupling between two moderately acidic primary or secondary C−H bonds, which are adjacent to an oxygen or nitrogen atom on one side, and benzylic or adjacent to a carbonyl group on the other side. A variety of valuable fused heterocycles were obtained from easily accessible ortho‐bromophenol and aniline precursors. The second C−H bond cleavage was successfully replaced with carbonyl insertion to generate other types of C(sp3)‐C(sp3) bonds.
A variety of fused heterocycles are obtained from easily accessible ortho‐bromophenol and aniline precursors by intramolecular coupling of two C(sp3)−H bonds, enabled by 1,4‐Pd shift from a trisubstituted aryl bromide. Unlike most C(sp3)−C(sp3) cross‐dehydrogenative couplings, this reaction operates under redox‐neutral conditions, with the C−Br bond acting as an internal oxidant.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>31397959</pmid><doi>10.1002/anie.201908460</doi><tpages>4</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-0847-8493</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | Acidic oxides Aniline Aromatic compounds Bonding Carbonyl compounds Carbonyl groups Carbonyls Couplings C−H activation Dehydrogenation domino reactions heterocycles Hydrogen bonds Palladium |
| title | Redox‐Neutral Coupling between Two C(sp3)−H Bonds Enabled by 1,4‐Palladium Shift for the Synthesis of Fused Heterocycles |
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