Chiral Lithium Amido Aryl Zincates: Simple and Efficient Chemo‐ and Enantio‐Selective Aryl Transfer Reagents
An enantioselective aryl transfer is promoted using chiral tricoordinated lithium amido aryl zincates that are easily accessible reagents and whose chiral appendage is simply recovered for reuse. The arylation reaction is run in good yields (60 % average on twenty substrates) and high enantiomeric e...
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description | An enantioselective aryl transfer is promoted using chiral tricoordinated lithium amido aryl zincates that are easily accessible reagents and whose chiral appendage is simply recovered for reuse. The arylation reaction is run in good yields (60 % average on twenty substrates) and high enantiomeric excesses (95 % ee average). This occurs whatever the ortho, meta, or para substituent borne by the substrate and a complete chemoselectivity is observed with respect to the aldehyde function. Sensitive groups such as nitriles, esters, ketones, and enolisable substrates resist to the action of the ate reagent, warranting a large scope to this methodology.
Chemo‐ and enantio‐selective nucleophilic aryl transfer: The key reactant is a chiral tricoordinated lithium amido aryl zincate of which the chiral appendage is simply recovered and reused. The arylation leaves intact sensitive functions such as esters, nitriles, ketones or enolisable sites, while running with aldehyde groups in good yields and high ee values, this whatever the ortho, meta, or para substituent borne by the substrate if aromatic. |
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Chemo‐ and enantio‐selective nucleophilic aryl transfer: The key reactant is a chiral tricoordinated lithium amido aryl zincate of which the chiral appendage is simply recovered and reused. The arylation leaves intact sensitive functions such as esters, nitriles, ketones or enolisable sites, while running with aldehyde groups in good yields and high ee values, this whatever the ortho, meta, or para substituent borne by the substrate if aromatic.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201813510</identifier><identifier>PMID: 30653791</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>(R)-Neobenodine ; (R)-Orphenadrine ; Aromatic compounds ; Chemical Sciences ; chiral lithium amido zincate ; Cyanide ; Enantiomers ; enantioselective aryl transfer ; Esters ; Ketones ; Lithium ; Nitriles ; nucleophilic 1,2 arylation ; Organic chemistry ; Reagents ; Substrates ; Zincates</subject><ispartof>Angewandte Chemie International Edition, 2019-03, Vol.58 (10), p.3193-3197</ispartof><rights>2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4070-c50146039cace4d9d9e9cdaa6543897f254b525d948d11145509e54035ea92133</citedby><cites>FETCH-LOGICAL-c4070-c50146039cace4d9d9e9cdaa6543897f254b525d948d11145509e54035ea92133</cites><orcidid>0000-0001-8152-7370 ; 0000-0002-4137-3079 ; 0000-0001-8623-0533</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.201813510$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201813510$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>230,314,776,780,881,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/30653791$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.science/hal-02060072$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Chaumont‐Olive, Pauline</creatorcontrib><creatorcontrib>Rouen, Mathieu</creatorcontrib><creatorcontrib>Barozzino‐Consiglio, Gabriella</creatorcontrib><creatorcontrib>Ben Abdeladhim, Amel</creatorcontrib><creatorcontrib>Maddaluno, Jacques</creatorcontrib><creatorcontrib>Harrison‐Marchand, Anne</creatorcontrib><title>Chiral Lithium Amido Aryl Zincates: Simple and Efficient Chemo‐ and Enantio‐Selective Aryl Transfer Reagents</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>An enantioselective aryl transfer is promoted using chiral tricoordinated lithium amido aryl zincates that are easily accessible reagents and whose chiral appendage is simply recovered for reuse. The arylation reaction is run in good yields (60 % average on twenty substrates) and high enantiomeric excesses (95 % ee average). This occurs whatever the ortho, meta, or para substituent borne by the substrate and a complete chemoselectivity is observed with respect to the aldehyde function. Sensitive groups such as nitriles, esters, ketones, and enolisable substrates resist to the action of the ate reagent, warranting a large scope to this methodology.
Chemo‐ and enantio‐selective nucleophilic aryl transfer: The key reactant is a chiral tricoordinated lithium amido aryl zincate of which the chiral appendage is simply recovered and reused. The arylation leaves intact sensitive functions such as esters, nitriles, ketones or enolisable sites, while running with aldehyde groups in good yields and high ee values, this whatever the ortho, meta, or para substituent borne by the substrate if aromatic.</description><subject>(R)-Neobenodine</subject><subject>(R)-Orphenadrine</subject><subject>Aromatic compounds</subject><subject>Chemical Sciences</subject><subject>chiral lithium amido zincate</subject><subject>Cyanide</subject><subject>Enantiomers</subject><subject>enantioselective aryl transfer</subject><subject>Esters</subject><subject>Ketones</subject><subject>Lithium</subject><subject>Nitriles</subject><subject>nucleophilic 1,2 arylation</subject><subject>Organic chemistry</subject><subject>Reagents</subject><subject>Substrates</subject><subject>Zincates</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNqFkc9u1DAQhy0EoqVw5YgscSmHbGdiO4m5RauFVlpRiZYLF8t1Jqyr_FnspGhvPALPyJM025RF4sLJ49E3n2b0Y-w1wgIB0jPbeVqkgAUKhfCEHaNKMRF5Lp5OtRQiyQuFR-xFjLcTXxSQPWdHAjIlco3HbLvc-GAbvvbDxo8tL1tf9bwMu4Z_9Z2zA8X3_Mq324a47Sq-qmvvPHUDX26o7X___DW3O9sNfv-9oobc4O9ollwH28WaAv9M9ts0Fl-yZ7VtIr16fE_Ylw-r6-V5sr78eLEs14mTkEPiFKDMQGhnHclKV5q0q6zNlBSFzutUyRuVqkrLokJEqRRoUhKEIqtTFOKEvZu9G9uYbfCtDTvTW2_Oy7XZ9yCFDCBP73BiT2d2G_rvI8XBtD46ahrbUT9Gk2KuJWh80L79B73tx9BNl0xUobJCQJFN1GKmXOhjDFQfNkAw-9zMPjdzyG0aePOoHW9aqg74n6AmQM_AD9_Q7j86U366WP2V3wM3paNI</recordid><startdate>20190304</startdate><enddate>20190304</enddate><creator>Chaumont‐Olive, Pauline</creator><creator>Rouen, Mathieu</creator><creator>Barozzino‐Consiglio, Gabriella</creator><creator>Ben Abdeladhim, Amel</creator><creator>Maddaluno, Jacques</creator><creator>Harrison‐Marchand, Anne</creator><general>Wiley Subscription Services, Inc</general><general>Wiley-VCH Verlag</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><scope>1XC</scope><orcidid>https://orcid.org/0000-0001-8152-7370</orcidid><orcidid>https://orcid.org/0000-0002-4137-3079</orcidid><orcidid>https://orcid.org/0000-0001-8623-0533</orcidid></search><sort><creationdate>20190304</creationdate><title>Chiral Lithium Amido Aryl Zincates: Simple and Efficient Chemo‐ and Enantio‐Selective Aryl Transfer Reagents</title><author>Chaumont‐Olive, Pauline ; Rouen, Mathieu ; Barozzino‐Consiglio, Gabriella ; Ben Abdeladhim, Amel ; Maddaluno, Jacques ; Harrison‐Marchand, Anne</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4070-c50146039cace4d9d9e9cdaa6543897f254b525d948d11145509e54035ea92133</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>(R)-Neobenodine</topic><topic>(R)-Orphenadrine</topic><topic>Aromatic compounds</topic><topic>Chemical Sciences</topic><topic>chiral lithium amido zincate</topic><topic>Cyanide</topic><topic>Enantiomers</topic><topic>enantioselective aryl transfer</topic><topic>Esters</topic><topic>Ketones</topic><topic>Lithium</topic><topic>Nitriles</topic><topic>nucleophilic 1,2 arylation</topic><topic>Organic chemistry</topic><topic>Reagents</topic><topic>Substrates</topic><topic>Zincates</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Chaumont‐Olive, Pauline</creatorcontrib><creatorcontrib>Rouen, Mathieu</creatorcontrib><creatorcontrib>Barozzino‐Consiglio, Gabriella</creatorcontrib><creatorcontrib>Ben Abdeladhim, Amel</creatorcontrib><creatorcontrib>Maddaluno, Jacques</creatorcontrib><creatorcontrib>Harrison‐Marchand, Anne</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>Hyper Article en Ligne (HAL)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Chaumont‐Olive, Pauline</au><au>Rouen, Mathieu</au><au>Barozzino‐Consiglio, Gabriella</au><au>Ben Abdeladhim, Amel</au><au>Maddaluno, Jacques</au><au>Harrison‐Marchand, Anne</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Chiral Lithium Amido Aryl Zincates: Simple and Efficient Chemo‐ and Enantio‐Selective Aryl Transfer Reagents</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2019-03-04</date><risdate>2019</risdate><volume>58</volume><issue>10</issue><spage>3193</spage><epage>3197</epage><pages>3193-3197</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>An enantioselective aryl transfer is promoted using chiral tricoordinated lithium amido aryl zincates that are easily accessible reagents and whose chiral appendage is simply recovered for reuse. The arylation reaction is run in good yields (60 % average on twenty substrates) and high enantiomeric excesses (95 % ee average). This occurs whatever the ortho, meta, or para substituent borne by the substrate and a complete chemoselectivity is observed with respect to the aldehyde function. Sensitive groups such as nitriles, esters, ketones, and enolisable substrates resist to the action of the ate reagent, warranting a large scope to this methodology.
Chemo‐ and enantio‐selective nucleophilic aryl transfer: The key reactant is a chiral tricoordinated lithium amido aryl zincate of which the chiral appendage is simply recovered and reused. The arylation leaves intact sensitive functions such as esters, nitriles, ketones or enolisable sites, while running with aldehyde groups in good yields and high ee values, this whatever the ortho, meta, or para substituent borne by the substrate if aromatic.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>30653791</pmid><doi>10.1002/anie.201813510</doi><tpages>5</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0001-8152-7370</orcidid><orcidid>https://orcid.org/0000-0002-4137-3079</orcidid><orcidid>https://orcid.org/0000-0001-8623-0533</orcidid></addata></record> |
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subjects | (R)-Neobenodine (R)-Orphenadrine Aromatic compounds Chemical Sciences chiral lithium amido zincate Cyanide Enantiomers enantioselective aryl transfer Esters Ketones Lithium Nitriles nucleophilic 1,2 arylation Organic chemistry Reagents Substrates Zincates |
title | Chiral Lithium Amido Aryl Zincates: Simple and Efficient Chemo‐ and Enantio‐Selective Aryl Transfer Reagents |
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