Synthesis of Allyl Cyanamides and N-Cyanoindoles via the Palladium-Catalyzed Three-Component Coupling Reaction
The palladium-catalyzed three-component coupling reaction (TCCR) of aryl isocyanides, allyl methyl carbonate, and trimethylsilyl azide was conducted in the presence of Pd2(dba)3·CHCl3 (2.5 mol %) and dppe (1,2-bis(diphenylphosphino)ethane) (10 mol %). Allyl aryl cyanamides with a wide variety of fun...
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| Veröffentlicht in: | Journal of the American Chemical Society 2002-10, Vol.124 (40), p.11940-11945 |
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| container_title | Journal of the American Chemical Society |
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| creator | Kamijo, Shin Yamamoto, Yoshinori |
| description | The palladium-catalyzed three-component coupling reaction (TCCR) of aryl isocyanides, allyl methyl carbonate, and trimethylsilyl azide was conducted in the presence of Pd2(dba)3·CHCl3 (2.5 mol %) and dppe (1,2-bis(diphenylphosphino)ethane) (10 mol %). Allyl aryl cyanamides with a wide variety of functional groups were obtained in excellent yields. This palladium-catalyzed TCCR was further utilized for the synthesis of N-cyanoindoles. The reaction of 2-alkynylisocyanobenzenes, allyl methyl carbonate, and trimethylsilyl azide in the presence of Pd2(dba)3·CHCl3 (2.5 mol %) and tri(2-furyl)phosphine (10 mol %) at higher temperatures afforded N-cyanoindoles in good to allowable yields. (η3-Allyl)(η3-cyanamido)palladium complex, an analogue of the bis-π-allylpalladium complex, is a key intermediate in the TCCR, and a π-allylpalladium mimic of the Curtius rearrangement is involved to generate the (η3-allyl)(η3-cyanamido)palladium intermediate. |
| doi_str_mv | 10.1021/ja0272742 |
| format | Article |
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Allyl aryl cyanamides with a wide variety of functional groups were obtained in excellent yields. This palladium-catalyzed TCCR was further utilized for the synthesis of N-cyanoindoles. The reaction of 2-alkynylisocyanobenzenes, allyl methyl carbonate, and trimethylsilyl azide in the presence of Pd2(dba)3·CHCl3 (2.5 mol %) and tri(2-furyl)phosphine (10 mol %) at higher temperatures afforded N-cyanoindoles in good to allowable yields. (η3-Allyl)(η3-cyanamido)palladium complex, an analogue of the bis-π-allylpalladium complex, is a key intermediate in the TCCR, and a π-allylpalladium mimic of the Curtius rearrangement is involved to generate the (η3-allyl)(η3-cyanamido)palladium intermediate.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja0272742</identifier><identifier>PMID: 12358538</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Crystallography, X-Ray ; Cyanamide - chemical synthesis ; Cyanamide - chemistry ; Cyanides - chemical synthesis ; Cyanides - chemistry ; Indoles - chemical synthesis ; Indoles - chemistry ; Molecular Structure ; Palladium - chemistry</subject><ispartof>Journal of the American Chemical Society, 2002-10, Vol.124 (40), p.11940-11945</ispartof><rights>Copyright © 2002 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a415t-39ee17c9082d00e93b038dd1b978e93d31872d791cd312e0c27d1dc0b7c8ac283</citedby><cites>FETCH-LOGICAL-a415t-39ee17c9082d00e93b038dd1b978e93d31872d791cd312e0c27d1dc0b7c8ac283</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja0272742$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja0272742$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2752,27055,27903,27904,56716,56766</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/12358538$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kamijo, Shin</creatorcontrib><creatorcontrib>Yamamoto, Yoshinori</creatorcontrib><title>Synthesis of Allyl Cyanamides and N-Cyanoindoles via the Palladium-Catalyzed Three-Component Coupling Reaction</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>The palladium-catalyzed three-component coupling reaction (TCCR) of aryl isocyanides, allyl methyl carbonate, and trimethylsilyl azide was conducted in the presence of Pd2(dba)3·CHCl3 (2.5 mol %) and dppe (1,2-bis(diphenylphosphino)ethane) (10 mol %). Allyl aryl cyanamides with a wide variety of functional groups were obtained in excellent yields. This palladium-catalyzed TCCR was further utilized for the synthesis of N-cyanoindoles. The reaction of 2-alkynylisocyanobenzenes, allyl methyl carbonate, and trimethylsilyl azide in the presence of Pd2(dba)3·CHCl3 (2.5 mol %) and tri(2-furyl)phosphine (10 mol %) at higher temperatures afforded N-cyanoindoles in good to allowable yields. (η3-Allyl)(η3-cyanamido)palladium complex, an analogue of the bis-π-allylpalladium complex, is a key intermediate in the TCCR, and a π-allylpalladium mimic of the Curtius rearrangement is involved to generate the (η3-allyl)(η3-cyanamido)palladium intermediate.</description><subject>Crystallography, X-Ray</subject><subject>Cyanamide - chemical synthesis</subject><subject>Cyanamide - chemistry</subject><subject>Cyanides - chemical synthesis</subject><subject>Cyanides - chemistry</subject><subject>Indoles - chemical synthesis</subject><subject>Indoles - chemistry</subject><subject>Molecular Structure</subject><subject>Palladium - chemistry</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2002</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkE1v1DAQhi1ERbeFA38A-QISBxd_JLFzrCJKkVa0YhcJcbG89iz14tjbOEENvx5XuyoXTvaMH78zehB6zegFo5x92BnKJZcVf4YWrOaU1Iw3z9GCUsqJVI04RWc570pZccVeoFPGRa1qoRYoruY43kH2GactvgxhDribTTS9d5CxiQ5_IY-N5KNLobR-e4PLD3xrQjDOTz3pzGjC_AccXt8NAKRL_T5FiCPu0rQPPv7EX8HY0af4Ep1sTcjw6nieo29XH9fdNVnefPrcXS6JqVg9EtECMGlbqrijFFqxoUI5xzatVKVyginJnWyZLVcO1HLpmLN0I60ylitxjt4dcvdDup8gj7r32ULZOEKaspacVaKYKuD7A2iHlPMAW70ffG-GWTOqH-XqJ7mFfXMMnTY9uH_k0WYByAHweYSHp3cz_NKNFLLW69uVblZN9eNq-V03hX974I3NepemIRYn_xn8F5UEj30</recordid><startdate>20021009</startdate><enddate>20021009</enddate><creator>Kamijo, Shin</creator><creator>Yamamoto, Yoshinori</creator><general>American Chemical Society</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>7X8</scope></search><sort><creationdate>20021009</creationdate><title>Synthesis of Allyl Cyanamides and N-Cyanoindoles via the Palladium-Catalyzed Three-Component Coupling Reaction</title><author>Kamijo, Shin ; Yamamoto, Yoshinori</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a415t-39ee17c9082d00e93b038dd1b978e93d31872d791cd312e0c27d1dc0b7c8ac283</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2002</creationdate><topic>Crystallography, X-Ray</topic><topic>Cyanamide - chemical synthesis</topic><topic>Cyanamide - chemistry</topic><topic>Cyanides - chemical synthesis</topic><topic>Cyanides - chemistry</topic><topic>Indoles - chemical synthesis</topic><topic>Indoles - chemistry</topic><topic>Molecular Structure</topic><topic>Palladium - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kamijo, Shin</creatorcontrib><creatorcontrib>Yamamoto, Yoshinori</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>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kamijo, Shin</au><au>Yamamoto, Yoshinori</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis of Allyl Cyanamides and N-Cyanoindoles via the Palladium-Catalyzed Three-Component Coupling Reaction</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2002-10-09</date><risdate>2002</risdate><volume>124</volume><issue>40</issue><spage>11940</spage><epage>11945</epage><pages>11940-11945</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>The palladium-catalyzed three-component coupling reaction (TCCR) of aryl isocyanides, allyl methyl carbonate, and trimethylsilyl azide was conducted in the presence of Pd2(dba)3·CHCl3 (2.5 mol %) and dppe (1,2-bis(diphenylphosphino)ethane) (10 mol %). Allyl aryl cyanamides with a wide variety of functional groups were obtained in excellent yields. This palladium-catalyzed TCCR was further utilized for the synthesis of N-cyanoindoles. The reaction of 2-alkynylisocyanobenzenes, allyl methyl carbonate, and trimethylsilyl azide in the presence of Pd2(dba)3·CHCl3 (2.5 mol %) and tri(2-furyl)phosphine (10 mol %) at higher temperatures afforded N-cyanoindoles in good to allowable yields. (η3-Allyl)(η3-cyanamido)palladium complex, an analogue of the bis-π-allylpalladium complex, is a key intermediate in the TCCR, and a π-allylpalladium mimic of the Curtius rearrangement is involved to generate the (η3-allyl)(η3-cyanamido)palladium intermediate.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>12358538</pmid><doi>10.1021/ja0272742</doi><tpages>6</tpages></addata></record> |
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| ispartof | Journal of the American Chemical Society, 2002-10, Vol.124 (40), p.11940-11945 |
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| language | eng |
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| source | ACS Publications; MEDLINE |
| subjects | Crystallography, X-Ray Cyanamide - chemical synthesis Cyanamide - chemistry Cyanides - chemical synthesis Cyanides - chemistry Indoles - chemical synthesis Indoles - chemistry Molecular Structure Palladium - chemistry |
| title | Synthesis of Allyl Cyanamides and N-Cyanoindoles via the Palladium-Catalyzed Three-Component Coupling Reaction |
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