{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,17]],"date-time":"2026-07-17T20:06:27Z","timestamp":1784318787161,"version":"3.55.0"},"reference-count":50,"publisher":"Wiley","issue":"10","license":[{"start":{"date-parts":[[2021,9,12]],"date-time":"2021-09-12T00:00:00Z","timestamp":1631404800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100008457","name":"University of Virginia","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100008457","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Helvetica Chimica Acta"],"published-print":{"date-parts":[[2021,10]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Reactions are described for complexes of the form WTp(NO)(PMe<jats:sub>3<\/jats:sub>)(\u03b7<jats:sup>2<\/jats:sup>\u2010arene) and various amines, where the arene is benzene or benzene with an electron\u2010withdrawing substituent (CF<jats:sub>3<\/jats:sub>, SO<jats:sub>2<\/jats:sub>Ph, SO<jats:sub>2<\/jats:sub>Me). The arene complex is first protonated to form an \u03b7<jats:sup>2<\/jats:sup>\u2010arenium species, which then selectively adds the amine. The resulting \u03b7<jats:sup>2<\/jats:sup>\u20105\u2010amino\u20101,3\u2010cyclohexadiene complexes can then be subjected to the same sequence with a second nucleophile to form 3\u2010aminocyclohexene complexes, where up to three stereocenters originate from the arene carbons. Alternatively, 1,3\u2010cyclohexadiene complexes containing an ester group at the 5 position (also prepared from an arene) can be treated with acid followed by an amine to form trisubstituted 3\u2010aminocyclohexenes. When the amine is primary, ring closure can occur to form a <jats:italic>cis<\/jats:italic>\u2010fused bicyclic \u03b3\u2010lactam. Highly functionalized cyclohexenes can be liberated from the tungsten through oxidative decomplexation. The potential utility of this methodology is demonstrated in the synthesis of the alkaloid \u03b3\u2010lycorane. An enantioenriched synthesis of a lactam precursor to \u03b3\u2010lycorane is also described. This compound is prepared from an enantioenriched version of the tungsten benzene complex. Regio\u2010 and stereochemical assignments for the reported compounds are supported by detailed 2D\u2010NMR analysis and 13 molecular structure determinations (SC\u2010XRD).<\/jats:p>","DOI":"10.1002\/hlca.202100103","type":"journal-article","created":{"date-parts":[[2021,8,10]],"date-time":"2021-08-10T18:41:21Z","timestamp":1628620881000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Hydroamination of Dihapto\u2010Coordinated Benzene and Diene Complexes of Tungsten: Fundamental Studies and the Synthesis of \u03b3\u2010Lycorane"],"prefix":"10.1002","volume":"104","author":[{"given":"Katy B.","family":"Wilson","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Virginia  Charlottesville Virginia 22904 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hannah S.","family":"Nedzbala","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Virginia  Charlottesville Virginia 22904 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Spenser R.","family":"Simpson","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Virginia  Charlottesville Virginia 22904 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Megan N.","family":"Ericson","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Virginia  Charlottesville Virginia 22904 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Karl S.","family":"Westendorff","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Virginia  Charlottesville Virginia 22904 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mahendra D.","family":"Chordia","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Virginia  Charlottesville Virginia 22904 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Diane A.","family":"Dickie","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Virginia  Charlottesville Virginia 22904 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0939-6980","authenticated-orcid":false,"given":"W. Dean","family":"Harman","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Virginia  Charlottesville Virginia 22904 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2021,9,12]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1186\/s13065-019-0606-7"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr300389u"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja4092819"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200404261"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr9902852"},{"key":"e_1_2_7_6_1","doi-asserted-by":"crossref","unstructured":"E.\u2005P. K\u00fcndig \u2018Transition Metal Arene \u03c0-Complexes in Organic Synthesis and Catalysis. Topics in Organometallic Chemistry\u2019 Vol. 7 Springer Berlin Heidelberg 2004.","DOI":"10.1007\/b76615"},{"key":"e_1_2_7_7_1","doi-asserted-by":"crossref","unstructured":"M.\u2005F. Semmelhack \u2018Transition Metal Arene Complexes: Nucleophilic Addition\u2019 Chapter\u20059.1 in \u2018Comprehensive Organometallic Chemistry II\u2019 Vol. 12 Eds. E.\u2005W. Abel F.\u2005G.\u2005A. Stone G. Wilkinson Pergamon Oxford 1995 pp. 979\u20131015.","DOI":"10.1016\/B978-008046519-7.00133-7"},{"key":"e_1_2_7_8_1","doi-asserted-by":"crossref","unstructured":"M.\u2005F. Semmelhack A. Chlenov \u2018(Arene)Cr(CO)3Complexes: Aromatic Nucleophilic Substitution\u2019 in \u2018Transition Metal Arene \u03c0-Complexes in Organic Synthesis and Catalysis. Topics in Organometallic Chemistry\u2019 Vol. 7 Ed. E.\u2005P. 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