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The one\u2010pot sequence involves a series of carefully orchestrated steps: addition, formylation, tautomerization, and dehydration, with CuCN catalyzing a key equilibration of a formyl imine to an N\u2010formyl enamine. The resulting aromatic alkeneisocyanides, that are otherwise challenging to synthesize, engage in an unusual [4+2]\u2010type cycloaddition\/1,3\u2010H shift\/decyanation sequence to afford substituted naphthalenes.<\/jats:p>","DOI":"10.1002\/anie.201607806","type":"journal-article","created":{"date-parts":[[2016,10,25]],"date-time":"2016-10-25T07:33:18Z","timestamp":1477380798000},"page":"14770-14773","source":"Crossref","is-referenced-by-count":9,"title":["Direct Conversion of Nitriles into Alkene \u201cIsonitriles\u201d"],"prefix":"10.1002","volume":"55","author":[{"given":"Yajun","family":"Li","sequence":"first","affiliation":[{"name":"Department of Chemistry Drexel University  32 S. 32 nd Street Philadelphia PA 19104-2875 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9637-0246","authenticated-orcid":false,"given":"Fraser F.","family":"Fleming","sequence":"additional","affiliation":[{"name":"Department of Chemistry Drexel University  32 S. 32 nd Street Philadelphia PA 19104-2875 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2016,10,25]]},"reference":[{"key":"e_1_2_2_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527652532"},{"key":"e_1_2_2_2_1","unstructured":"\u00a0"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.3762\/bjoc.10.179"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100233r"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.2174\/0929867033368600"},{"key":"e_1_2_2_6_1","unstructured":"Although numerous isocyanides are commercially available in milligram quantities less than a dozen are readily available at commodity prices with 1-isocyanocyclohex-1-ene as the only readily available example of an alkeneisocyanide."},{"key":"e_1_2_2_7_1","unstructured":"\u00a0"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo900414n"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1990-21181"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)99237-2"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(88)85157-8"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)98240-7"},{"key":"e_1_2_2_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b00483"},{"key":"e_1_2_2_14_1","unstructured":"\u00a0"},{"key":"e_1_2_2_15_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)96674-8"},{"key":"e_1_2_2_16_2","doi-asserted-by":"crossref","unstructured":"A. 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L.","year":"1994"},{"key":"e_1_2_2_40_1","unstructured":"Addition of MeLi to 4-iodobenzonitrile and 4-bromobenzonitrile failed to afford the corresponding metalloimines. Inverse addition of 4-chlorobenzonitrile to the methyllithium-CuCN solution was crucial to provide6\u2009jin reasonable yield."},{"key":"e_1_2_2_41_1","unstructured":"2-Cyanopyridine afforded theN-formyl enamine but the dehydration is problematic possibly because of complexation to the pyridine nitrogen and the formamide. Thiophene-2-carbonitrile and 1-methyl-1H-indole-3-carbonitrile afforded alkeneisocyanide6\u2009q(27\u2009%) and alkeneisocyanide6\u2009r(31\u2009%) respectively. Cinnamonitrile afforded alkeneisocyanide6\u2009min 31\u2009% yield."},{"key":"e_1_2_2_42_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19901231110"},{"key":"e_1_2_2_43_1","unstructured":"No reaction of6\u2009aor6\u2009hwas observed with 3 4-dihydro-2H-pyran ethyl acrylate or benzylidenemalononitrile at temperatures up to 110\u2009\u00b0C."},{"key":"e_1_2_2_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/np800164s"},{"key":"e_1_2_2_45_1","unstructured":"Reducing the amount of CuMeSal to 5\u2005mol\u2009% led to 90\u2009% conversion and doubled the reaction time whereas with 1\u2005mol\u2009% CuMeSal the reaction stalled at 30\u2009% conversion after 10\u2005h at 110\u2009\u00b0C."},{"key":"e_1_2_2_46_1","unstructured":"No [4+2] dimerization was observed with electron-deficient alkeneisocyanide6\u2009jor the methyl-substituted alkeneisocyanide6\u2009b."},{"key":"e_1_2_2_47_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201101170"},{"key":"e_1_2_2_48_1","unstructured":"\u00a0"},{"key":"e_1_2_2_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr500380d"},{"key":"e_1_2_2_50_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201400017"},{"key":"e_1_2_2_51_1","unstructured":"Prepared in 53\u2009% yield following the standard procedure. See the Supporting Information for details."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201607806","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.201607806","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201607806","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.201607806","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.201607806","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,8,30]],"date-time":"2023-08-30T18:52:58Z","timestamp":1693421578000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.201607806"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2016,10,25]]},"references-count":54,"journal-issue":{"issue":"47","published-print":{"date-parts":[[2016,11,14]]}},"alternative-id":["10.1002\/anie.201607806"],"URL":"https:\/\/doi.org\/10.1002\/anie.201607806","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2016,10,25]]}}}