{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,26]],"date-time":"2026-03-26T17:52:14Z","timestamp":1774547534495,"version":"3.50.1"},"reference-count":68,"publisher":"Wiley","issue":"24","license":[{"start":{"date-parts":[[2009,4,28]],"date-time":"2009-04-28T00:00:00Z","timestamp":1240876800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2009,6,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:bold>[2+3] Cycloadditions!<\/jats:bold> The metal\u2010mediated [2+3] cycloaddition of acyclic [<jats:sup>\u2212<\/jats:sup>O<jats:sup>+<\/jats:sup>N(R<jats:sup>2<\/jats:sup>)\uf8fe(H)R<jats:sup>3<\/jats:sup>] and nonaromatic cyclic nitrones [<jats:sup>\u2212<\/jats:sup>O<jats:sup>+<\/jats:sup>N<jats:sup><jats:italic>a<\/jats:italic><\/jats:sup>\uf8feCHCH<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>C<jats:sup><jats:italic>b<\/jats:italic><\/jats:sup>Me<jats:sub>2<\/jats:sub>(N<jats:sup><jats:italic>a<\/jats:italic><\/jats:sup>\uf8ffC<jats:sup><jats:italic>b<\/jats:italic><\/jats:sup>)] to palladium\u2010bound isonitriles <jats:italic>cis<\/jats:italic>\u2010[PdCl<jats:sub>2<\/jats:sub>(C\uf8fdNR)<jats:sub>2<\/jats:sub>] proceeds under mild conditions to furnish novel heterocyclic carbene complexes, which then undergo N\uf8ffO bond rupture to give imino complexes and free isocyanates (see scheme).<jats:boxed-text content-type=\"graphic\" position=\"anchor\"><jats:graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" mimetype=\"image\/gif\" position=\"anchor\" specific-use=\"enlarged-web-image\" xlink:href=\"graphic\/mcontent.gif\"><jats:alt-text>magnified image<\/jats:alt-text><\/jats:graphic><\/jats:boxed-text><\/jats:p><jats:p>The reactions between equimolar amounts of <jats:italic>cis<\/jats:italic>\u2010[PdCl<jats:sub>2<\/jats:sub>(C\uf8fdNR)<jats:sub>2<\/jats:sub>] (R=cyclohexyl (Cy) <jats:bold>1<\/jats:bold>, <jats:italic>t<\/jats:italic>Bu <jats:bold>2<\/jats:bold>, 2,6\u2010Me<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub> (Xyl) <jats:bold>3<\/jats:bold>) and the acyclic nitrones O<jats:sup>+<\/jats:sup>N(R<jats:sup>2<\/jats:sup>)\uf8feC(H)R<jats:sup>3<\/jats:sup> (R<jats:sup>2<\/jats:sup>=Me <jats:bold>5<\/jats:bold>, R<jats:sup>2<\/jats:sup>=CH<jats:sub>2<\/jats:sub>Ph <jats:bold>6<\/jats:bold>, R<jats:sup>3<\/jats:sup><jats:bold>=<\/jats:bold>4\u2010MeC<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>) proceeded in C<jats:sub>6<\/jats:sub>H<jats:sub>6<\/jats:sub> at 5\u2009\u00b0C for around 4\u2005h and then the reaction systems were maintained at 20\u201325\u2009\u00b0C for 20\u2005h to provide the carbene complexes [PdCl<jats:sub>2<\/jats:sub>{C(ONR<jats:sup>2<\/jats:sup>C<jats:sup><jats:italic>c<\/jats:italic><\/jats:sup>HR<jats:sup>3<\/jats:sup>)=N<jats:sup><jats:italic>d<\/jats:italic><\/jats:sup>R}(C\uf8fdNR)(C<jats:sup><jats:italic>c<\/jats:italic><\/jats:sup>\uf8ffN<jats:sup><jats:italic>d<\/jats:italic><\/jats:sup>)] (<jats:bold>8<\/jats:bold>\u2013<jats:bold>13<\/jats:bold>) in good yields (54\u201370\u2009%). The latter species originated from the previously unreported metal\u2010mediated [2+3] cycloaddition of nitrones to coordinated isonitriles. For the reactions of <jats:italic>cis<\/jats:italic>\u2010[PdCl<jats:sub>2<\/jats:sub>(C\uf8fdNR)<jats:sub>2<\/jats:sub>] (<jats:bold>1<\/jats:bold>\u2013<jats:bold>3<\/jats:bold>) and <jats:bold>5<\/jats:bold> or <jats:bold>6<\/jats:bold> performed in C<jats:sub>6<\/jats:sub>H<jats:sub>6<\/jats:sub> at 20\u201325\u2009\u00b0C, the selectivity of the cycloaddition was lost, and the reactions gave mixtures of <jats:bold>8<\/jats:bold>\u2013<jats:bold>13<\/jats:bold> and the complexes [PdCl<jats:sub>2<\/jats:sub>{N(R<jats:sup>2<\/jats:sup>)\uf8feCHR<jats:sup>3<\/jats:sup>}(C\uf8fdNR)] (<jats:bold>14<\/jats:bold>\u2013<jats:bold>19<\/jats:bold>, ca. 75\u2009%) derived from intramolecular deoxygenation of the nitrones. The reactions of equimolar amounts of <jats:italic>cis<\/jats:italic>\u2010[PdCl<jats:sub>2<\/jats:sub>(C\uf8fdNR)<jats:sub>2<\/jats:sub>] (<jats:bold>1<\/jats:bold>\u2013<jats:bold>3<\/jats:bold> and R=4\u2010MeOC<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub> <jats:bold>4<\/jats:bold>) and the nonaromatic cyclic nitrone <jats:sup>\u2212<\/jats:sup>O<jats:sup>+<\/jats:sup>N<jats:sup><jats:italic>a<\/jats:italic><\/jats:sup>\uf8feCHCH<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>C<jats:sup><jats:italic>b<\/jats:italic><\/jats:sup>Me<jats:sub>2<\/jats:sub>(N<jats:sup><jats:italic>a<\/jats:italic><\/jats:sup>\uf8ffC<jats:sup><jats:italic>b<\/jats:italic><\/jats:sup>) (<jats:bold>7<\/jats:bold>) in CHCl<jats:sub>3<\/jats:sub> at 5\u2009\u00b0C for around 2\u2005h led to the carbene species [PdCl<jats:sub>2<\/jats:sub>{C(ON<jats:sup><jats:italic>a<\/jats:italic><\/jats:sup>CMe<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>C<jats:sup><jats:italic>b<\/jats:italic><\/jats:sup>H)=N<jats:sup><jats:italic>e<\/jats:italic><\/jats:sup>R}(C\uf8fdNR)(N<jats:sup><jats:italic>a<\/jats:italic><\/jats:sup>\uf8ffC<jats:sup><jats:italic>b<\/jats:italic><\/jats:sup>)(C<jats:sup><jats:italic>b<\/jats:italic><\/jats:sup>\uf8ffN<jats:sup><jats:italic>e<\/jats:italic><\/jats:sup>)] (<jats:bold>21<\/jats:bold>\u2013<jats:bold>24<\/jats:bold>), isolated in yields of 78\u201392\u2009%. When the reactions of <jats:italic>cis<\/jats:italic>\u2010[PdCl<jats:sub>2<\/jats:sub>(C\uf8fdNR)<jats:sub>2<\/jats:sub>] (<jats:bold>1<\/jats:bold>\u2013<jats:bold>4<\/jats:bold>) and <jats:bold>7<\/jats:bold> (1:1 molar ratio) were performed in CHCl<jats:sub>3<\/jats:sub> at 20\u201325\u2009\u00b0C for around 1\u2005h, the carbenes <jats:bold>21<\/jats:bold>\u2013<jats:bold>24<\/jats:bold> and the complexes [PdCl<jats:sub>2<\/jats:sub>{N<jats:sup><jats:italic>f<\/jats:italic><\/jats:sup>CMe<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>C<jats:sup><jats:italic>g<\/jats:italic><\/jats:sup>H}(C\uf8fdNR)(N<jats:sup><jats:italic>f<\/jats:italic><\/jats:sup>\uf8ffC<jats:sup><jats:italic>g<\/jats:italic><\/jats:sup>)] (<jats:bold>25<\/jats:bold>\u2013<jats:bold>28<\/jats:bold>, ca. 35\u2009%), derived from the deoxygenation of <jats:bold>7<\/jats:bold>, were identified by ESI<jats:sup>+<\/jats:sup>\u2010MS and <jats:sup>1<\/jats:sup>H\u2005NMR analysis (after redissolution in CDCl<jats:sub>3<\/jats:sub>). The reactions of <jats:italic>cis<\/jats:italic>\u2010[PdCl<jats:sub>2<\/jats:sub>(C\uf8fdNR)<jats:sub>2<\/jats:sub>] (<jats:bold>1<\/jats:bold>\u2013<jats:bold>4<\/jats:bold>) and <jats:bold>7<\/jats:bold> (1:2 molar ratio) in CHCl<jats:sub>3<\/jats:sub> at 5\u2009\u00b0C furnished mixtures of [PdCl<jats:sub>2<\/jats:sub>{C(ON<jats:sup><jats:italic>a<\/jats:italic><\/jats:sup>CMe<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>C<jats:sup><jats:italic>b<\/jats:italic><\/jats:sup>H)\uf8feN<jats:sup><jats:italic>e<\/jats:italic><\/jats:sup>R}(N<jats:sup><jats:italic>f<\/jats:italic><\/jats:sup>CMe<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>C<jats:sup><jats:italic>g<\/jats:italic><\/jats:sup>H)(N<jats:sup><jats:italic>a<\/jats:italic><\/jats:sup>\uf8ffC<jats:sup><jats:italic>b<\/jats:italic><\/jats:sup>)(C<jats:sup><jats:italic>b<\/jats:italic><\/jats:sup>\uf8ffN<jats:sup><jats:italic>e<\/jats:italic><\/jats:sup>)(N<jats:sup><jats:italic>f<\/jats:italic><\/jats:sup>\uf8ffC<jats:sup><jats:italic>g<\/jats:italic><\/jats:sup>)] (<jats:bold>29<\/jats:bold>\u2013<jats:bold>32<\/jats:bold>; ca. 25\u201330\u2009%), <jats:bold>25<\/jats:bold>\u2013<jats:bold>28<\/jats:bold> (ca. 10\u201315\u2009%), and [PdCl<jats:sub>2<\/jats:sub>(ON<jats:sup><jats:italic>a<\/jats:italic><\/jats:sup>CMe<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>C<jats:sup><jats:italic>b<\/jats:italic><\/jats:sup>H)<jats:sub>2<\/jats:sub>(N<jats:sup><jats:italic>a<\/jats:italic><\/jats:sup>\uf8ffC<jats:sup><jats:italic>b<\/jats:italic><\/jats:sup>)]. The same reactions at room temperature afforded the complex [PdCl<jats:sub>2<\/jats:sub>(N<jats:sup><jats:italic>f<\/jats:italic><\/jats:sup>CMe<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>C<jats:sup><jats:italic>g<\/jats:italic><\/jats:sup>H)<jats:sub>2<\/jats:sub>(N<jats:sup><jats:italic>f<\/jats:italic><\/jats:sup>\uf8ffC<jats:sup><jats:italic>g<\/jats:italic><\/jats:sup>)] (<jats:bold>33<\/jats:bold>; ca. 20\u2009%) in a mixture with <jats:bold>29<\/jats:bold>\u2013<jats:bold>32<\/jats:bold> (ca. 5\u201310\u2009%) and <jats:bold>25<\/jats:bold>\u2013<jats:bold>28<\/jats:bold>.<\/jats:p>","DOI":"10.1002\/chem.200802623","type":"journal-article","created":{"date-parts":[[2009,4,28]],"date-time":"2009-04-28T14:11:19Z","timestamp":1240927879000},"page":"5969-5978","source":"Crossref","is-referenced-by-count":54,"title":["Metal\u2010Mediated [2+3] Cycloaddition of Nitrones to Palladium\u2010Bound Isonitriles"],"prefix":"10.1002","volume":"15","author":[{"given":"Konstantin\u2005V.","family":"Luzyanin","sequence":"first","affiliation":[]},{"given":"Alexander\u2005G.","family":"Tskhovrebov","sequence":"additional","affiliation":[]},{"given":"M. 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