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Herein, we report that the lithium complex [(Ph<jats:sub>2<\/jats:sub>P(S))<jats:sub>2<\/jats:sub>CLi<jats:sub>2<\/jats:sub>(THF)]<jats:sub>2<\/jats:sub> <jats:bold>1<\/jats:bold> reacts with CO lead to C\u2212C bond formation and migration of a Ph<jats:sub>2<\/jats:sub>P(<jats:italic>S<\/jats:italic>)\u2010fragment affording <jats:bold>2<\/jats:bold>. Subsequent reaction with N<jats:sub>2<\/jats:sub>O results in oxidative cleavage of a P\u2212C bond affording [Ph<jats:sub>2<\/jats:sub>P(S)OLi(THF)<jats:sub>2<\/jats:sub>]<jats:sub>2<\/jats:sub> <jats:bold>4<\/jats:bold> and the anionic ketene\u2010derivative Ph<jats:sub>2<\/jats:sub>P(S)CCOLi(THF)<jats:sub>2<\/jats:sub> <jats:bold>5<\/jats:bold>. Heating <jats:bold>5<\/jats:bold> prompts cyclotrimerization giving the hexa\u2010substituted benzene derivative [Ph<jats:sub>2<\/jats:sub>P(S)CCOLi(THF)<jats:sub>2<\/jats:sub>]<jats:sub>3<\/jats:sub> <jats:bold>6<\/jats:bold> regioselectively. This transition metal\u2010free protocol to a hexa\u2010substituted benzene is viable on a gram scale and permits the incorporation of <jats:sup>13<\/jats:sup>C labels. The mechanisms of these reactions are detailed via extensive DFT computations.<\/jats:p>","DOI":"10.1002\/anie.202111486","type":"journal-article","created":{"date-parts":[[2021,9,24]],"date-time":"2021-09-24T15:01:55Z","timestamp":1632495715000},"page":"25281-25285","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":31,"title":["Reactions of a Dilithiomethane with CO and N<sub>2<\/sub>O: An Avenue to an Anionic Ketene and a Hexafunctionalized Benzene"],"prefix":"10.1002","volume":"60","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-3160-4862","authenticated-orcid":false,"given":"Maotong","family":"Xu","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Toronto  80 St. George St. Toronto Ontario M5S3H6 Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Tongtong","family":"Wang","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Toronto  80 St. 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