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We herein report a dearomative sequential addition of two nucleophiles to arene \u03c0\u2010bonds through umpolung of chromium\u2013arene complexes. This mode enables divergent dearomative carbonylation reactions of benzene derivatives by tolerating various nucleophiles in combination with alcohols or amines under CO\u2010gas\u2010free conditions, thus providing modular access to functionalized esters or amides. The tunable synthesis of 1,3\u2010 or 1,4\u2010cyclohexadienes as well as the construction of carbon quaternary centers further highlight the versatility of this dearomatization. Diverse late\u2010stage modifications and derivatizations towards synthetically challenging and bioactive molecules reveal the synthetic utility. A possible mechanism was proposed based on control experiments and intermediate tracking.<\/jats:p>","DOI":"10.1002\/anie.202403917","type":"journal-article","created":{"date-parts":[[2024,5,31]],"date-time":"2024-05-31T08:14:51Z","timestamp":1717143291000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":26,"title":["Umpolung\u2010Enabled Divergent Dearomative Carbonylations"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5398-8417","authenticated-orcid":false,"given":"Ming\u2010Yang","family":"Wang","sequence":"first","affiliation":[{"name":"Department of Chemistry Zhejiang University  Hangzhou 310058 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wei\u2010Long","family":"Zeng","sequence":"additional","affiliation":[{"name":"Department of Chemistry Zhejiang University  Hangzhou 310058 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lin","family":"Chen","sequence":"additional","affiliation":[{"name":"Department of Chemistry Zhejiang University  Hangzhou 310058 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yu\u2010Fei","family":"Yuan","sequence":"additional","affiliation":[{"name":"Department of Chemistry Zhejiang University  Hangzhou 310058 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8858-114X","authenticated-orcid":false,"given":"Wei","family":"Li","sequence":"additional","affiliation":[{"name":"Department of Chemistry Zhejiang University  Hangzhou 310058 China"},{"name":"State Key Laboratory of Elemento-Organic Chemistry Nankai University  Tianjin 300071 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,7,9]]},"reference":[{"key":"e_1_2_8_1_1","unstructured":"\u00a0"},{"key":"e_1_2_8_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm901241e"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2md20347b"},{"key":"e_1_2_8_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.drudis.2009.07.014"},{"key":"e_1_2_8_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm101356p"},{"key":"e_1_2_8_6_2","doi-asserted-by":"publisher","DOI":"10.1111\/cbdd.12260"},{"key":"e_1_2_8_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.0c00829"},{"key":"e_1_2_8_8_1","unstructured":"For selected reviews see:"},{"key":"e_1_2_8_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/9783527698479"},{"key":"e_1_2_8_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201204822"},{"key":"e_1_2_8_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscentsci.0c01651"},{"key":"e_1_2_8_12_2","doi-asserted-by":"publisher","DOI":"10.1039\/C9CS00311H"},{"key":"e_1_2_8_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201006017"},{"key":"e_1_2_8_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.1c00781"},{"key":"e_1_2_8_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201901229"},{"key":"e_1_2_8_16_2","doi-asserted-by":"publisher","DOI":"10.1039\/D2NP00042C"},{"key":"e_1_2_8_17_1","unstructured":"For selected reviews see:"},{"key":"e_1_2_8_18_2","doi-asserted-by":"publisher","DOI":"10.1039\/C8CS00389K"},{"key":"e_1_2_8_19_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2020.06.015"},{"key":"e_1_2_8_20_1","unstructured":"For reviews on dearomatizing agents of \u03b72-arene complexes see:"},{"key":"e_1_2_8_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr940316n"},{"key":"e_1_2_8_22_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(99)00249-0"},{"key":"e_1_2_8_23_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2004.03.013"},{"key":"e_1_2_8_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00480"},{"key":"e_1_2_8_25_1","unstructured":"For reviews on dearomatizing agents of \u03b76-arene complexes see:"},{"key":"e_1_2_8_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9902852"},{"key":"e_1_2_8_27_2","volume-title":"Topics in Organometallic Chemistry","author":"K\u00fcndig E. 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