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Carbene <jats:bold>4<\/jats:bold> reacts with benzene to afford two isomeric adducts, 10\u2010phenylbicyclo[6.3.0]undecapentaene (<jats:bold>10<\/jats:bold>) and tricyclo[9.3.0<jats:sup>3,\u200910<\/jats:sup>.0]heptadeca\u20101,3(10),4,6,8,12,14,16\u2010octaene (<jats:bold>11<\/jats:bold>). The reactivity toward benzene is a characteristic of an electrophilic aromatic carbene analogous to cyclopentadienylidene <jats:bold>1<\/jats:bold>. In contrast, the reaction of <jats:bold>4<\/jats:bold> with methanol produces 7\u2010methoxybicyclo[6.3.0]undeca\u20101,3,5,8,10\u2010pentaene (<jats:bold>15<\/jats:bold>). When [D<jats:sub>1<\/jats:sub>]methanol was employed as a reactant, the 10\u2010deuterated analogue was formed. The results clearly indicate the formation of bicyclo[6.3.0]undecapentaenyl cation (<jats:bold>7<\/jats:bold>) as a novel 10\u2009\u03c0\u2010electronic compound by protonation of <jats:bold>4<\/jats:bold>. Theoretical calculations indicate that the 2\u2010 and 7\u2010positions of the cation have the largest positive charge in the cation. Moreover, the carbene was generated in the presence of <jats:italic>tert\u2010<\/jats:italic>butyl hydroperoxide in aqueous tetrahydrofuran to afford azulene through oxidation of <jats:bold>7<\/jats:bold>, followed by decarbonylation. The nucleophilic property of carbene <jats:bold>3<\/jats:bold> is similar to that of cycloheptatrienylidene <jats:bold>2<\/jats:bold>. Thus, <jats:bold>4<\/jats:bold> can be regarded as a novel ambiphilic aromatic carbene.<\/jats:p>","DOI":"10.1002\/cplu.201700069","type":"journal-article","created":{"date-parts":[[2017,3,6]],"date-time":"2017-03-06T09:22:44Z","timestamp":1488792164000},"page":"1073-1077","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Bicyclo[6.3.0]undeca\u20101(11),2,4,6,8\u2010pentaen\u201010\u2010ylidene: An Aromatic Carbene with Ambiphilic Properties"],"prefix":"10.1002","volume":"82","author":[{"given":"Hiroyuki","family":"Ishikawa","sequence":"first","affiliation":[{"name":"Graduate School of Engineering University of Hyogo  2167 Shosha, Himeji Hyogo 671-2280 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jun\u2010ichi","family":"Nishida","sequence":"additional","affiliation":[{"name":"Graduate School of Engineering University of Hyogo  2167 Shosha, Himeji Hyogo 671-2280 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"suffix":"Jr.","given":"John W.","family":"Jones","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Center for Advanced Study University of Nevada  Reno NV 89557-0020 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Lawrence T.","family":"Scott","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Center for Advanced Study University of Nevada  Reno NV 89557-0020 USA"},{"name":"Merkert Chemistry Center Department of Chemistry Boston College  Chestnut Hill MA 02467-3860 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6997-4194","authenticated-orcid":false,"given":"Takeshi","family":"Kawase","sequence":"additional","affiliation":[{"name":"Graduate School of Engineering University of Hyogo  2167 Shosha, Himeji Hyogo 671-2280 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2017,3,22]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01065a053"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00407a040"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00409a065"},{"key":"e_1_2_7_5_1","unstructured":"\u00a0"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00988a060"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01051a036"},{"key":"e_1_2_7_8_1","first-page":"185","volume-title":"Modern Allene Chemistry, Vol.\u20051","author":"Christl M.","year":"2002"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00302a003"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/asia.201301307"},{"key":"e_1_2_7_11_1","unstructured":"[4n]Annuleno[4n]annulenes with 10\u2009\u03c0 electrons were also reported:"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)82117-1"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)87429-8"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac198658010007"},{"key":"e_1_2_7_15_1","unstructured":"\u00a0"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)83522-X"},{"key":"e_1_2_7_17_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)93635-9"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)93636-0"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198310031"},{"key":"e_1_2_7_19_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19830951212"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19861190307"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)70793-3"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00792a072"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.196900761"},{"key":"e_1_2_7_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19690810205"},{"key":"e_1_2_7_23_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.196900762"},{"key":"e_1_2_7_23_4","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19690810205"},{"key":"e_1_2_7_24_1","unstructured":"M.\u2005J. 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