New synthesis of multisubstituted cyanocyclopropanes by the intramolecular SN2 alkylation and 1,3-CC insertion reaction of magnesium carbenoids as the key reactions
Addition reaction of 1-chlorovinyl p-tolyl sulfoxides derived from ketones and aldehydes with lithium α-cyano carbanions gave nitrile adducts in high to quantitative yields. Treatment of the nitrile adducts derived from acetonitrile with excess i-PrMgCl in THF resulted in the formation of cyanocyclo...
Gespeichert in:
| Veröffentlicht in: | Tetrahedron 2012-03, Vol.68 (11), p.2481-2495 |
|---|---|
| Hauptverfasser: | , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 2495 |
|---|---|
| container_issue | 11 |
| container_start_page | 2481 |
| container_title | Tetrahedron |
| container_volume | 68 |
| creator | Saitoh, Hideki Watanabe, Tatsuya Kimura, Tsutomu Kato, Yuichi Satoh, Tsuyoshi |
| description | Addition reaction of 1-chlorovinyl p-tolyl sulfoxides derived from ketones and aldehydes with lithium α-cyano carbanions gave nitrile adducts in high to quantitative yields. Treatment of the nitrile adducts derived from acetonitrile with excess i-PrMgCl in THF resulted in the formation of cyanocyclopropanes via the intramolecular SN2 alkylation of the generated magnesium carbenoids. The intermediate of this reaction was proved to be a cyclopropylmagnesium chloride and was reactive with electrophiles to give multisubstituted cyanocyclopropanes. On the other hand, the reaction of the nitrile adducts derived from arylacetonitriles with i-PrMgCl resulted in the formation of 2-arylcyanocyclopropanes by the 1,3-carbon–carbon (1,3-CC) insertion reaction of the generated magnesium carbenoid intermediates. This reaction was found to proceed in a highly stereospecific manner. The key reactions, intramolecular SN2 alkylation and 1,3-CC insertion reaction of the magnesium carbenoids, are the first examples for the reaction of the magnesium carbenoids bearing a nitrile functional group.
[Display omitted] |
| doi_str_mv | 10.1016/j.tet.2012.01.059 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1744678850</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><els_id>S0040402012000993</els_id><sourcerecordid>1744678850</sourcerecordid><originalsourceid>FETCH-LOGICAL-c2710-e8c40058d9ea6a74f3fa4f6fc6c8e683aa8978903ebcd92b7e2a6703c42886463</originalsourceid><addsrcrecordid>eNp9kc2O1DAQhCMEEsPCA3DzBYkDCe3EcRxxQqPlR1otB-BsdZwOeDY_g9sB5X14UDwzqz1y6lbrq2qVKsteSigkSP32UESKRQmyLEAWULePsp1UWuW1kvpxtgNQkCso4Wn2jPkAAFKW1S77e0t_BG9z_EnsWSyDmNYxel47jj6ukXrhNpwXt7lxOYbliDOx6DaRBMLPMeC0jOTWEYP4elsKHO-2EaNfZoFzL-SbKt_vE8gUzsdA6M7L6RP-SGZ-nYTD0NG8-J4F8tn6jrYHlp9nTwYcmV7cz6vs-4frb_tP-c2Xj5_3729yVzYScjJOAdSmbwk1NmqoBlSDHpx2hrSpEE3bmBYq6lzfll1DJeoGKqdKY7TS1VX2-uKbgv5aiaOdPDsaxxR6WdnKRindGFNDQuUFdWFhDjTYY_AThs1KsKdG7MGmRuypEQvSpkaS5tW9PbLDcQg4O88PwrLWWjZQJ-7dhaOU9benYNl5mh31PpCLtl_8f778A2ITpFw</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1744678850</pqid></control><display><type>article</type><title>New synthesis of multisubstituted cyanocyclopropanes by the intramolecular SN2 alkylation and 1,3-CC insertion reaction of magnesium carbenoids as the key reactions</title><source>Elsevier ScienceDirect Journals</source><creator>Saitoh, Hideki ; Watanabe, Tatsuya ; Kimura, Tsutomu ; Kato, Yuichi ; Satoh, Tsuyoshi</creator><creatorcontrib>Saitoh, Hideki ; Watanabe, Tatsuya ; Kimura, Tsutomu ; Kato, Yuichi ; Satoh, Tsuyoshi</creatorcontrib><description>Addition reaction of 1-chlorovinyl p-tolyl sulfoxides derived from ketones and aldehydes with lithium α-cyano carbanions gave nitrile adducts in high to quantitative yields. Treatment of the nitrile adducts derived from acetonitrile with excess i-PrMgCl in THF resulted in the formation of cyanocyclopropanes via the intramolecular SN2 alkylation of the generated magnesium carbenoids. The intermediate of this reaction was proved to be a cyclopropylmagnesium chloride and was reactive with electrophiles to give multisubstituted cyanocyclopropanes. On the other hand, the reaction of the nitrile adducts derived from arylacetonitriles with i-PrMgCl resulted in the formation of 2-arylcyanocyclopropanes by the 1,3-carbon–carbon (1,3-CC) insertion reaction of the generated magnesium carbenoid intermediates. This reaction was found to proceed in a highly stereospecific manner. The key reactions, intramolecular SN2 alkylation and 1,3-CC insertion reaction of the magnesium carbenoids, are the first examples for the reaction of the magnesium carbenoids bearing a nitrile functional group.
[Display omitted]</description><identifier>ISSN: 0040-4020</identifier><identifier>EISSN: 1464-5416</identifier><identifier>DOI: 10.1016/j.tet.2012.01.059</identifier><identifier>CODEN: TETRAB</identifier><language>eng</language><publisher>Kidlington: Elsevier Ltd</publisher><subject>1,3-Carbon–carbon insertion reaction ; Acetonitrile ; Adducts ; Alicyclic compounds ; Alicyclic compounds, terpenoids, prostaglandins, steroids ; Alkylation ; Chemistry ; Chlorides ; Cyanocyclopropane ; Exact sciences and technology ; Formations ; Insertion ; Intramolecular alkylation ; Kinetics and mechanisms ; Magnesium ; Magnesium carbenoid ; Multisubstituted cyclopropane ; Nitriles ; Organic chemistry ; Preparations and properties ; Reactivity and mechanisms</subject><ispartof>Tetrahedron, 2012-03, Vol.68 (11), p.2481-2495</ispartof><rights>2012 Elsevier Ltd</rights><rights>2015 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c2710-e8c40058d9ea6a74f3fa4f6fc6c8e683aa8978903ebcd92b7e2a6703c42886463</citedby><cites>FETCH-LOGICAL-c2710-e8c40058d9ea6a74f3fa4f6fc6c8e683aa8978903ebcd92b7e2a6703c42886463</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/j.tet.2012.01.059$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,777,781,3537,27905,27906,45976</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=25661705$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Saitoh, Hideki</creatorcontrib><creatorcontrib>Watanabe, Tatsuya</creatorcontrib><creatorcontrib>Kimura, Tsutomu</creatorcontrib><creatorcontrib>Kato, Yuichi</creatorcontrib><creatorcontrib>Satoh, Tsuyoshi</creatorcontrib><title>New synthesis of multisubstituted cyanocyclopropanes by the intramolecular SN2 alkylation and 1,3-CC insertion reaction of magnesium carbenoids as the key reactions</title><title>Tetrahedron</title><description>Addition reaction of 1-chlorovinyl p-tolyl sulfoxides derived from ketones and aldehydes with lithium α-cyano carbanions gave nitrile adducts in high to quantitative yields. Treatment of the nitrile adducts derived from acetonitrile with excess i-PrMgCl in THF resulted in the formation of cyanocyclopropanes via the intramolecular SN2 alkylation of the generated magnesium carbenoids. The intermediate of this reaction was proved to be a cyclopropylmagnesium chloride and was reactive with electrophiles to give multisubstituted cyanocyclopropanes. On the other hand, the reaction of the nitrile adducts derived from arylacetonitriles with i-PrMgCl resulted in the formation of 2-arylcyanocyclopropanes by the 1,3-carbon–carbon (1,3-CC) insertion reaction of the generated magnesium carbenoid intermediates. This reaction was found to proceed in a highly stereospecific manner. The key reactions, intramolecular SN2 alkylation and 1,3-CC insertion reaction of the magnesium carbenoids, are the first examples for the reaction of the magnesium carbenoids bearing a nitrile functional group.
[Display omitted]</description><subject>1,3-Carbon–carbon insertion reaction</subject><subject>Acetonitrile</subject><subject>Adducts</subject><subject>Alicyclic compounds</subject><subject>Alicyclic compounds, terpenoids, prostaglandins, steroids</subject><subject>Alkylation</subject><subject>Chemistry</subject><subject>Chlorides</subject><subject>Cyanocyclopropane</subject><subject>Exact sciences and technology</subject><subject>Formations</subject><subject>Insertion</subject><subject>Intramolecular alkylation</subject><subject>Kinetics and mechanisms</subject><subject>Magnesium</subject><subject>Magnesium carbenoid</subject><subject>Multisubstituted cyclopropane</subject><subject>Nitriles</subject><subject>Organic chemistry</subject><subject>Preparations and properties</subject><subject>Reactivity and mechanisms</subject><issn>0040-4020</issn><issn>1464-5416</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2012</creationdate><recordtype>article</recordtype><recordid>eNp9kc2O1DAQhCMEEsPCA3DzBYkDCe3EcRxxQqPlR1otB-BsdZwOeDY_g9sB5X14UDwzqz1y6lbrq2qVKsteSigkSP32UESKRQmyLEAWULePsp1UWuW1kvpxtgNQkCso4Wn2jPkAAFKW1S77e0t_BG9z_EnsWSyDmNYxel47jj6ukXrhNpwXt7lxOYbliDOx6DaRBMLPMeC0jOTWEYP4elsKHO-2EaNfZoFzL-SbKt_vE8gUzsdA6M7L6RP-SGZ-nYTD0NG8-J4F8tn6jrYHlp9nTwYcmV7cz6vs-4frb_tP-c2Xj5_3729yVzYScjJOAdSmbwk1NmqoBlSDHpx2hrSpEE3bmBYq6lzfll1DJeoGKqdKY7TS1VX2-uKbgv5aiaOdPDsaxxR6WdnKRindGFNDQuUFdWFhDjTYY_AThs1KsKdG7MGmRuypEQvSpkaS5tW9PbLDcQg4O88PwrLWWjZQJ-7dhaOU9benYNl5mh31PpCLtl_8f778A2ITpFw</recordid><startdate>20120318</startdate><enddate>20120318</enddate><creator>Saitoh, Hideki</creator><creator>Watanabe, Tatsuya</creator><creator>Kimura, Tsutomu</creator><creator>Kato, Yuichi</creator><creator>Satoh, Tsuyoshi</creator><general>Elsevier Ltd</general><general>Elsevier</general><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>20120318</creationdate><title>New synthesis of multisubstituted cyanocyclopropanes by the intramolecular SN2 alkylation and 1,3-CC insertion reaction of magnesium carbenoids as the key reactions</title><author>Saitoh, Hideki ; Watanabe, Tatsuya ; Kimura, Tsutomu ; Kato, Yuichi ; Satoh, Tsuyoshi</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c2710-e8c40058d9ea6a74f3fa4f6fc6c8e683aa8978903ebcd92b7e2a6703c42886463</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2012</creationdate><topic>1,3-Carbon–carbon insertion reaction</topic><topic>Acetonitrile</topic><topic>Adducts</topic><topic>Alicyclic compounds</topic><topic>Alicyclic compounds, terpenoids, prostaglandins, steroids</topic><topic>Alkylation</topic><topic>Chemistry</topic><topic>Chlorides</topic><topic>Cyanocyclopropane</topic><topic>Exact sciences and technology</topic><topic>Formations</topic><topic>Insertion</topic><topic>Intramolecular alkylation</topic><topic>Kinetics and mechanisms</topic><topic>Magnesium</topic><topic>Magnesium carbenoid</topic><topic>Multisubstituted cyclopropane</topic><topic>Nitriles</topic><topic>Organic chemistry</topic><topic>Preparations and properties</topic><topic>Reactivity and mechanisms</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Saitoh, Hideki</creatorcontrib><creatorcontrib>Watanabe, Tatsuya</creatorcontrib><creatorcontrib>Kimura, Tsutomu</creatorcontrib><creatorcontrib>Kato, Yuichi</creatorcontrib><creatorcontrib>Satoh, Tsuyoshi</creatorcontrib><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Tetrahedron</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Saitoh, Hideki</au><au>Watanabe, Tatsuya</au><au>Kimura, Tsutomu</au><au>Kato, Yuichi</au><au>Satoh, Tsuyoshi</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>New synthesis of multisubstituted cyanocyclopropanes by the intramolecular SN2 alkylation and 1,3-CC insertion reaction of magnesium carbenoids as the key reactions</atitle><jtitle>Tetrahedron</jtitle><date>2012-03-18</date><risdate>2012</risdate><volume>68</volume><issue>11</issue><spage>2481</spage><epage>2495</epage><pages>2481-2495</pages><issn>0040-4020</issn><eissn>1464-5416</eissn><coden>TETRAB</coden><abstract>Addition reaction of 1-chlorovinyl p-tolyl sulfoxides derived from ketones and aldehydes with lithium α-cyano carbanions gave nitrile adducts in high to quantitative yields. Treatment of the nitrile adducts derived from acetonitrile with excess i-PrMgCl in THF resulted in the formation of cyanocyclopropanes via the intramolecular SN2 alkylation of the generated magnesium carbenoids. The intermediate of this reaction was proved to be a cyclopropylmagnesium chloride and was reactive with electrophiles to give multisubstituted cyanocyclopropanes. On the other hand, the reaction of the nitrile adducts derived from arylacetonitriles with i-PrMgCl resulted in the formation of 2-arylcyanocyclopropanes by the 1,3-carbon–carbon (1,3-CC) insertion reaction of the generated magnesium carbenoid intermediates. This reaction was found to proceed in a highly stereospecific manner. The key reactions, intramolecular SN2 alkylation and 1,3-CC insertion reaction of the magnesium carbenoids, are the first examples for the reaction of the magnesium carbenoids bearing a nitrile functional group.
[Display omitted]</abstract><cop>Kidlington</cop><pub>Elsevier Ltd</pub><doi>10.1016/j.tet.2012.01.059</doi><tpages>15</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0040-4020 |
| ispartof | Tetrahedron, 2012-03, Vol.68 (11), p.2481-2495 |
| issn | 0040-4020 1464-5416 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_1744678850 |
| source | Elsevier ScienceDirect Journals |
| subjects | 1,3-Carbon–carbon insertion reaction Acetonitrile Adducts Alicyclic compounds Alicyclic compounds, terpenoids, prostaglandins, steroids Alkylation Chemistry Chlorides Cyanocyclopropane Exact sciences and technology Formations Insertion Intramolecular alkylation Kinetics and mechanisms Magnesium Magnesium carbenoid Multisubstituted cyclopropane Nitriles Organic chemistry Preparations and properties Reactivity and mechanisms |
| title | New synthesis of multisubstituted cyanocyclopropanes by the intramolecular SN2 alkylation and 1,3-CC insertion reaction of magnesium carbenoids as the key reactions |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-18T20%3A19%3A20IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=New%20synthesis%20of%20multisubstituted%20cyanocyclopropanes%20by%20the%20intramolecular%20SN2%20alkylation%20and%201,3-CC%20insertion%20reaction%20of%20magnesium%20carbenoids%20as%20the%20key%20reactions&rft.jtitle=Tetrahedron&rft.au=Saitoh,%20Hideki&rft.date=2012-03-18&rft.volume=68&rft.issue=11&rft.spage=2481&rft.epage=2495&rft.pages=2481-2495&rft.issn=0040-4020&rft.eissn=1464-5416&rft.coden=TETRAB&rft_id=info:doi/10.1016/j.tet.2012.01.059&rft_dat=%3Cproquest_cross%3E1744678850%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=1744678850&rft_id=info:pmid/&rft_els_id=S0040402012000993&rfr_iscdi=true |