{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,13]],"date-time":"2026-10-13T09:14:27Z","timestamp":1791882867295,"version":"4.3.4"},"reference-count":83,"publisher":"Wiley","issue":"18","license":[{"start":{"date-parts":[[2025,3,2]],"date-time":"2025-03-02T00:00:00Z","timestamp":1740873600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100000057","name":"National Institute of General Medical Sciences","doi-asserted-by":"publisher","award":["R01GM109054"],"award-info":[{"award-number":["R01GM109054"]}],"id":[{"id":"10.13039\/100000057","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2025,4,25]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    Insertion of arynes into cyclic C\u2212C bonds provides a straightforward approach for ring expansion with an\n                    <jats:italic>ortho<\/jats:italic>\n                    \u2010phenylene moiety; however, the current scope of substrates has been restricted to enolizable ketones. Here we report the first example of aryne\u2010insertion into non\u2010enolizable ketones through Pd\u2010catalyzed C\u2212C bond activation of benzocyclobutenones. 2\u2010Haloaryl boronates were employed as an unconventional aryne precursor. The reaction shows a wide substrate scope and high functional group tolerance. The mechanistic studies reveal an interesting dual role of the Pd catalyst for both aryne generation and C\u2212C bond activation.\n                  <\/jats:p>","DOI":"10.1002\/anie.202500148","type":"journal-article","created":{"date-parts":[[2025,2,19]],"date-time":"2025-02-19T15:39:16Z","timestamp":1739979556000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Ring Expansion via Palladium\u2010Catalyzed Aryne Insertion into C\u2212C Bonds of Benzocyclobutenones"],"prefix":"10.1002","volume":"64","author":[{"given":"Cole J.","family":"Wagner","sequence":"first","affiliation":[{"name":"Department of Chemistry The University of Chicago  5735 S. Ellis Ave. Chicago IL 60637"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1331-6015","authenticated-orcid":false,"given":"Guangbin","family":"Dong","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Chicago  5735 S. Ellis Ave. Chicago IL 60637"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,3,2]]},"reference":[{"key":"e_1_2_3_1_1","unstructured":"For reviews on ring expansion see:"},{"key":"e_1_2_3_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS01396J"},{"key":"e_1_2_3_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1OB00259G"},{"key":"e_1_2_3_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100295j"},{"key":"e_1_2_3_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/9783527830237.ch19"},{"key":"e_1_2_3_6_1","unstructured":"For reviews on C\u2212C Activation see:"},{"key":"e_1_2_3_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/B308864M"},{"key":"e_1_2_3_8_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-642-55055-3"},{"key":"e_1_2_3_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00138"},{"key":"e_1_2_3_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6CC04359C"},{"key":"e_1_2_3_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b03210"},{"key":"e_1_2_3_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.6b00599"},{"key":"e_1_2_3_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.trechm.2019.12.002"},{"key":"e_1_2_3_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.2c02667"},{"key":"e_1_2_3_15_1","unstructured":"For examples of \u201ccut-and-sew\u201d C\u2212C activation of four-membered ketones see:"},{"key":"e_1_2_3_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja021062n"},{"key":"e_1_2_3_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja8008715"},{"key":"e_1_2_3_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201202771"},{"key":"e_1_2_3_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201405834"},{"key":"e_1_2_3_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201310100"},{"key":"e_1_2_3_21_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.1989"},{"key":"e_1_2_3_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b09799"},{"key":"e_1_2_3_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b11120"},{"key":"e_1_2_3_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b09344"},{"key":"e_1_2_3_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c05647"},{"key":"e_1_2_3_26_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-021-23344-0"},{"key":"e_1_2_3_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202202703"},{"key":"e_1_2_3_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c04244"},{"key":"e_1_2_3_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c00063"},{"key":"e_1_2_3_30_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202405838"},{"key":"e_1_2_3_31_2","author":"Ma J.","year":"2024","journal-title":"Angew. Chem. Int. Ed."},{"key":"e_1_2_3_32_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-024-01120-9"},{"key":"e_1_2_3_33_1","doi-asserted-by":"publisher","DOI":"10.1016\/B978-0-323-85153-4.00004-6"},{"key":"e_1_2_3_34_1","unstructured":"For examples of aryne insertion reactions into C\u2212C bonds see:"},{"key":"e_1_2_3_35_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)86935-5"},{"key":"e_1_2_3_36_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199517211"},{"key":"e_1_2_3_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja050859m"},{"key":"e_1_2_3_38_2","doi-asserted-by":"publisher","DOI":"10.1039\/b505392g"},{"key":"e_1_2_3_39_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2023.05.032"},{"key":"e_1_2_3_40_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.8b01058"},{"key":"e_1_2_3_41_1","unstructured":"For reports on the formation of oligomers of arynes see:"},{"key":"e_1_2_3_42_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00948a017"},{"key":"e_1_2_3_43_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)89439-9"},{"key":"e_1_2_3_44_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19981016)37:19<2659::AID-ANIE2659>3.0.CO;2-4"},{"key":"e_1_2_3_45_1","unstructured":"For additional selected examples of the use of benzocyclobutenones in metal-catalyzed C\u2212C activation reactions see:"},{"key":"e_1_2_3_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b04691"},{"key":"e_1_2_3_47_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201503461"},{"key":"e_1_2_3_48_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201500458"},{"key":"e_1_2_3_49_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aao0453"},{"key":"e_1_2_3_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00158a009"},{"key":"e_1_2_3_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00037a047"},{"key":"e_1_2_3_52_1","unstructured":"For selected examples of the synthesis of metal-aryne complexes from (2-haloaryl)boronates or its use in Pd-catalyzed annulation reactions see:"},{"key":"e_1_2_3_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0264091"},{"key":"e_1_2_3_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol5006246"},{"key":"e_1_2_3_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.3c00103"},{"key":"e_1_2_3_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/acsorginorgau.3c00046"},{"key":"e_1_2_3_57_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.adi1606"},{"key":"e_1_2_3_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.4c00257"},{"key":"e_1_2_3_59_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.4c04873"},{"key":"e_1_2_3_60_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b03213"},{"key":"e_1_2_3_61_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b03833"},{"key":"e_1_2_3_62_1","unstructured":"\u00a0"},{"key":"e_1_2_3_63_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b07667"},{"key":"e_1_2_3_64_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-021-00746-7"},{"key":"e_1_2_3_65_1","unstructured":"For selected examples of the synthesis of phenanthrenones via C\u2212H functionalization see:"},{"key":"e_1_2_3_66_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja1026248"},{"key":"e_1_2_3_67_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja806681z"},{"key":"e_1_2_3_68_2","doi-asserted-by":"publisher","DOI":"10.1039\/D3SC01298K"},{"key":"e_1_2_3_69_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.2c00161"},{"key":"e_1_2_3_70_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr000024o"},{"key":"e_1_2_3_71_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.0c01011"},{"key":"e_1_2_3_72_1","unstructured":"The use of \u03b1 unsubstituted or mono-substituted BCBs as substrates gave complex reaction mixtures. For details of unsuccessful substrates see Supporting Information."},{"key":"e_1_2_3_73_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b02462"},{"key":"e_1_2_3_74_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201100035"},{"key":"e_1_2_3_75_1","unstructured":"Deposition number 2414009 contains the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service."},{"key":"e_1_2_3_76_1","unstructured":"Note that migratory insertion of the acyl group (instead of the aryl group) could also be possible."},{"key":"e_1_2_3_77_1","unstructured":"\u00a0"},{"key":"e_1_2_3_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar800040u"},{"key":"e_1_2_3_79_2","first-page":"1","volume-title":"C-H Activation","author":"Martins A.","year":"2010"},{"key":"e_1_2_3_80_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.6b00165"},{"key":"e_1_2_3_81_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.9b00079"},{"key":"e_1_2_3_82_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-0037-1611057"},{"key":"e_1_2_3_83_1","unstructured":"Pd(II) complexIII involved in both proposed mechanisms has three coordination sites occupied by two carbon ligands and one aryne ligand. Thus it only has one open coordination site for phosphine binding. Given that Pd(II) prefers a four-coordinated square planar geometry bidentate ligands would likely hinder the formation of complexIII. This could be the possible reason that this reaction benefits from less bulky monodentate ligands."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202500148","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,6,30]],"date-time":"2025-06-30T10:19:08Z","timestamp":1751278748000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202500148"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,3,2]]},"references-count":83,"journal-issue":{"issue":"18","published-print":{"date-parts":[[2025,4,25]]}},"alternative-id":["10.1002\/anie.202500148"],"URL":"https:\/\/doi.org\/10.1002\/anie.202500148","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,3,2]]},"assertion":[{"value":"2025-01-02","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-03-02","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202500148"}}