Ethynylbenziodazolones (EBZ) as Electrophilic Alkynylation Reagents for the Highly Enantioselective Copper‐Catalyzed Oxyalkynylation of Diazo Compounds
Ethynylbenziodoxol(on)e (EBX) cyclic hypervalent iodine reagents are now established reagents for the alkynylation of radicals and nucleophiles, yet they present limited possibilities for further structure and reactivity modification. Herein, the first synthesis is reported for the corresponding eth...
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Veröffentlicht in: | Chemistry : a European journal 2019-07, Vol.25 (40), p.9522-9528 |
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creator | Hari, Durga Prasad Schouwey, Lionel Barber, Verity Scopelliti, Rosario Fadaei‐Tirani, Farzaneh Waser, Jerome |
description | Ethynylbenziodoxol(on)e (EBX) cyclic hypervalent iodine reagents are now established reagents for the alkynylation of radicals and nucleophiles, yet they present limited possibilities for further structure and reactivity modification. Herein, the first synthesis is reported for the corresponding ethynylbenziodazolone (EBZ) reagents, in which the oxygen atom in the iodoheterocycle is replaced by a nitrogen atom. The substituent on the nitrogen enables further fine‐tuning of the reagent structure and reactivity. EBZ reagents are obtained easily from the corresponding benzamides by using a one‐step procedure, and display reactivity comparable to that of EBX reagents. In particular, they are applied in an asymmetric copper‐catalyzed oxyalkynylation of diazo compounds, which proceeds in high yield and enantioselectivity for a broad range of substituents on the diazo compounds and the alkyne.
Enantioselective reagents: Ethynylbenziodazolone (EBZ) cyclic hypervalent iodine reagents are synthesized for the first time, and display similar structure and reactivity to the established ethynylbenziodoxolone (EBX) reagents. They are used in the oxyalkynylation of diazo compounds to access imidate derivatives in high yield and enantioselectivity for a broad scope of diazo compounds and alkynes (see figure). |
doi_str_mv | 10.1002/chem.201900950 |
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Enantioselective reagents: Ethynylbenziodazolone (EBZ) cyclic hypervalent iodine reagents are synthesized for the first time, and display similar structure and reactivity to the established ethynylbenziodoxolone (EBX) reagents. They are used in the oxyalkynylation of diazo compounds to access imidate derivatives in high yield and enantioselectivity for a broad scope of diazo compounds and alkynes (see figure).</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.201900950</identifier><identifier>PMID: 30958592</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Alkynes ; carbenes ; catalysis ; Chemistry ; Copper ; Copper compounds ; diazo compounds ; Enantiomers ; enantioselectivity ; hypervalent iodine ; Iodine ; Nitrogen ; Nucleophiles ; Reactivity ; Reagents</subject><ispartof>Chemistry : a European journal, 2019-07, Vol.25 (40), p.9522-9528</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-c5160-7a22c60221c573e829b6d4bd2d3b94baa0c44f1fd7af89d9569abd5ed7dc9d2d3</citedby><cites>FETCH-LOGICAL-c5160-7a22c60221c573e829b6d4bd2d3b94baa0c44f1fd7af89d9569abd5ed7dc9d2d3</cites><orcidid>0000-0002-4570-914X ; 0000-0002-0734-8427</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.201900950$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.201900950$$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/30958592$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Hari, Durga Prasad</creatorcontrib><creatorcontrib>Schouwey, Lionel</creatorcontrib><creatorcontrib>Barber, Verity</creatorcontrib><creatorcontrib>Scopelliti, Rosario</creatorcontrib><creatorcontrib>Fadaei‐Tirani, Farzaneh</creatorcontrib><creatorcontrib>Waser, Jerome</creatorcontrib><title>Ethynylbenziodazolones (EBZ) as Electrophilic Alkynylation Reagents for the Highly Enantioselective Copper‐Catalyzed Oxyalkynylation of Diazo Compounds</title><title>Chemistry : a European journal</title><addtitle>Chemistry</addtitle><description>Ethynylbenziodoxol(on)e (EBX) cyclic hypervalent iodine reagents are now established reagents for the alkynylation of radicals and nucleophiles, yet they present limited possibilities for further structure and reactivity modification. Herein, the first synthesis is reported for the corresponding ethynylbenziodazolone (EBZ) reagents, in which the oxygen atom in the iodoheterocycle is replaced by a nitrogen atom. The substituent on the nitrogen enables further fine‐tuning of the reagent structure and reactivity. EBZ reagents are obtained easily from the corresponding benzamides by using a one‐step procedure, and display reactivity comparable to that of EBX reagents. In particular, they are applied in an asymmetric copper‐catalyzed oxyalkynylation of diazo compounds, which proceeds in high yield and enantioselectivity for a broad range of substituents on the diazo compounds and the alkyne.
Enantioselective reagents: Ethynylbenziodazolone (EBZ) cyclic hypervalent iodine reagents are synthesized for the first time, and display similar structure and reactivity to the established ethynylbenziodoxolone (EBX) reagents. They are used in the oxyalkynylation of diazo compounds to access imidate derivatives in high yield and enantioselectivity for a broad scope of diazo compounds and alkynes (see figure).</description><subject>Alkynes</subject><subject>carbenes</subject><subject>catalysis</subject><subject>Chemistry</subject><subject>Copper</subject><subject>Copper compounds</subject><subject>diazo compounds</subject><subject>Enantiomers</subject><subject>enantioselectivity</subject><subject>hypervalent iodine</subject><subject>Iodine</subject><subject>Nitrogen</subject><subject>Nucleophiles</subject><subject>Reactivity</subject><subject>Reagents</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNqF0bFu1TAUBmALUdFLYWVElljaIbeOEyfXYwmBW6lVJQQLS-TYJ42LY6dxAs2deARWXo8nwdEtBbEwneU7_znSj9CLmKxjQuipbKFbUxJzQjgjj9AqZjSOkjxjj9GK8DSPMpbwQ_TU-xsSTJYkT9BhEvCGcbpCP8qxne1sarA77ZTYOeMseHxcvv50goXHpQE5Dq5vtdESn5nPixajdha_B3ENdvS4cQMeW8Bbfd2aGZdW2AA8LKv6C-DC9T0MP799L8QozLwDha_uZvF3lmvwGx2uB9v1brLKP0MHjTAent_PI_Txbfmh2EYXV-_Oi7OLSLI4I1EuKJUZoTSWLE9gQ3mdqbRWVCU1T2shiEzTJm5ULpoNV5xlXNSKgcqV5Is6Qsf73H5wtxP4seq0l2CMsOAmX1FKWErynCWBvvqH3rhpsOG7oDLGkvAQDWq9V3Jw3g_QVP2gOzHMVUyqpbRqKa16KC0svLyPneoO1AP_3VIAfA--agPzf-KqYlte_gn_BZ6zqEE</recordid><startdate>20190717</startdate><enddate>20190717</enddate><creator>Hari, Durga Prasad</creator><creator>Schouwey, Lionel</creator><creator>Barber, Verity</creator><creator>Scopelliti, Rosario</creator><creator>Fadaei‐Tirani, Farzaneh</creator><creator>Waser, Jerome</creator><general>Wiley Subscription Services, Inc</general><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><orcidid>https://orcid.org/0000-0002-4570-914X</orcidid><orcidid>https://orcid.org/0000-0002-0734-8427</orcidid></search><sort><creationdate>20190717</creationdate><title>Ethynylbenziodazolones (EBZ) as Electrophilic Alkynylation Reagents for the Highly Enantioselective Copper‐Catalyzed Oxyalkynylation of Diazo Compounds</title><author>Hari, Durga Prasad ; Schouwey, Lionel ; Barber, Verity ; Scopelliti, Rosario ; Fadaei‐Tirani, Farzaneh ; Waser, Jerome</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5160-7a22c60221c573e829b6d4bd2d3b94baa0c44f1fd7af89d9569abd5ed7dc9d2d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Alkynes</topic><topic>carbenes</topic><topic>catalysis</topic><topic>Chemistry</topic><topic>Copper</topic><topic>Copper compounds</topic><topic>diazo compounds</topic><topic>Enantiomers</topic><topic>enantioselectivity</topic><topic>hypervalent iodine</topic><topic>Iodine</topic><topic>Nitrogen</topic><topic>Nucleophiles</topic><topic>Reactivity</topic><topic>Reagents</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Hari, Durga Prasad</creatorcontrib><creatorcontrib>Schouwey, Lionel</creatorcontrib><creatorcontrib>Barber, Verity</creatorcontrib><creatorcontrib>Scopelliti, Rosario</creatorcontrib><creatorcontrib>Fadaei‐Tirani, Farzaneh</creatorcontrib><creatorcontrib>Waser, Jerome</creatorcontrib><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><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Hari, Durga Prasad</au><au>Schouwey, Lionel</au><au>Barber, Verity</au><au>Scopelliti, Rosario</au><au>Fadaei‐Tirani, Farzaneh</au><au>Waser, Jerome</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Ethynylbenziodazolones (EBZ) as Electrophilic Alkynylation Reagents for the Highly Enantioselective Copper‐Catalyzed Oxyalkynylation of Diazo Compounds</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chemistry</addtitle><date>2019-07-17</date><risdate>2019</risdate><volume>25</volume><issue>40</issue><spage>9522</spage><epage>9528</epage><pages>9522-9528</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>Ethynylbenziodoxol(on)e (EBX) cyclic hypervalent iodine reagents are now established reagents for the alkynylation of radicals and nucleophiles, yet they present limited possibilities for further structure and reactivity modification. Herein, the first synthesis is reported for the corresponding ethynylbenziodazolone (EBZ) reagents, in which the oxygen atom in the iodoheterocycle is replaced by a nitrogen atom. The substituent on the nitrogen enables further fine‐tuning of the reagent structure and reactivity. EBZ reagents are obtained easily from the corresponding benzamides by using a one‐step procedure, and display reactivity comparable to that of EBX reagents. In particular, they are applied in an asymmetric copper‐catalyzed oxyalkynylation of diazo compounds, which proceeds in high yield and enantioselectivity for a broad range of substituents on the diazo compounds and the alkyne.
Enantioselective reagents: Ethynylbenziodazolone (EBZ) cyclic hypervalent iodine reagents are synthesized for the first time, and display similar structure and reactivity to the established ethynylbenziodoxolone (EBX) reagents. They are used in the oxyalkynylation of diazo compounds to access imidate derivatives in high yield and enantioselectivity for a broad scope of diazo compounds and alkynes (see figure).</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>30958592</pmid><doi>10.1002/chem.201900950</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0002-4570-914X</orcidid><orcidid>https://orcid.org/0000-0002-0734-8427</orcidid><oa>free_for_read</oa></addata></record> |
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subjects | Alkynes carbenes catalysis Chemistry Copper Copper compounds diazo compounds Enantiomers enantioselectivity hypervalent iodine Iodine Nitrogen Nucleophiles Reactivity Reagents |
title | Ethynylbenziodazolones (EBZ) as Electrophilic Alkynylation Reagents for the Highly Enantioselective Copper‐Catalyzed Oxyalkynylation of Diazo Compounds |
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