{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T16:58:46Z","timestamp":1790701126768,"version":"4.1.0"},"reference-count":71,"publisher":"Wiley","issue":"48","license":[{"start":{"date-parts":[[2025,10,7]],"date-time":"2025-10-07T00:00:00Z","timestamp":1759795200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2025,10,7]],"date-time":"2025-10-07T00:00:00Z","timestamp":1759795200000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100001352","name":"National University of Singapore","doi-asserted-by":"publisher","award":["A\u20108001466\u201300\u201300"],"award-info":[{"award-number":["A\u20108001466\u201300\u201300"]}],"id":[{"id":"10.13039\/501100001352","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":[[2025,11,24]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Triarylbismuth(V)\u2010mediated arylation represents an important approach for synthesizing a wide range of \u03b1\u2010arylated ketones and enol derivatives. Since the seminal work by Barton and colleagues in the 1980s, these C\u2500C bond\u2010forming transformations have been extensively explored. Despite significant progress, asymmetric variants of these reactions have yet to be developed. In this study, we document a sequential reaction consisting of bismuth\u2010mediated \u03b1\u2010arylation of allene ketones and an enantioselective protonation of \u03b1\u2010arylated alkynyl ketones, leveraging the isomerization between allenyl and alkynyl intermediates. Our approach relies on a reversible\/irreversible isomerization sequence comprising three distinct stages. The process initiates with the generation of enolates through reversible isomerization, followed by oxidative arylation and a subsequent enantioselective, irreversible isomerization to yield \u03b1\u2010arylated allenones. Both experimental results and theoretical studies support our mechanistic proposal. The sequential bismuth(V)\u2010mediated arylation and enantioselective proton transfer is conceptually significant, as coupling bismuth chemistry with asymmetric catalysis may open new avenues for organobismuth(V) chemistry in enantioselective transformations and extend its utility in synthetic organic chemistry.<\/jats:p>","DOI":"10.1002\/anie.202517136","type":"journal-article","created":{"date-parts":[[2025,10,7]],"date-time":"2025-10-07T13:07:12Z","timestamp":1759842432000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Enantioselective Synthesis of \u03b1\u2010Arylated Allene Ketones Through Sequential Bismuth(V)\u2010mediated Arylation and Organocatalytic Protonation"],"prefix":"10.1002","volume":"64","author":[{"given":"Kun","family":"Zhu","sequence":"first","affiliation":[{"name":"Department of Chemistry National University of Singapore  Singapore 117543 Singapore"},{"name":"Energy and Environmental Nanotech Platform National University of Singapore (Suzhou) Research Institute  Suzhou 215123 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuli","family":"Sun","sequence":"additional","affiliation":[{"name":"Department of Chemistry National University of Singapore  Singapore 117543 Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yunhan","family":"Ma","sequence":"additional","affiliation":[{"name":"Department of Chemistry National University of Singapore  Singapore 117543 Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zugen","family":"Wu","sequence":"additional","affiliation":[{"name":"Department of Chemistry National University of Singapore  Singapore 117543 Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5730-166X","authenticated-orcid":false,"given":"Yixin","family":"Lu","sequence":"additional","affiliation":[{"name":"Department of Chemistry National University of Singapore  Singapore 117543 Singapore"},{"name":"Energy and Environmental Nanotech Platform National University of Singapore (Suzhou) Research Institute  Suzhou 215123 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,10,7]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.609"},{"key":"e_1_2_7_2_1","volume-title":"Organobismuth Chemistry","author":"Suzuki H.","year":"2001"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1108\/00368790210431709"},{"key":"e_1_2_7_4_1","volume-title":"USGS Minerals Yearbook: Bismuth","author":"Singerling S. A.","year":"2018"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/c0cs00206b"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-642-27239-4"},{"key":"e_1_2_7_7_1","first-page":"706","author":"Barton D. H. R.","year":"1979","journal-title":"J. Chem. Soc. Chem. Commun."},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(81)85042-9"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00097a005"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja030150k"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja048987i"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-0036-1589482"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.aaz2258"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.202000667"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.1c04897"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-023-01229-7"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202315046"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c05598"},{"key":"e_1_2_7_19_1","author":"Tang N.","year":"2025","journal-title":"Angew. Chem., Int. Ed."},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202418367"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1039\/C39800000246"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1039\/p19850002657"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1039\/c39820000732"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/p19850002667"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)99281-5"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00305a014"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo9905928"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol901963v"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1039\/p19920001593"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-020-0425-4"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202210840"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.oprd.3c00509"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2QO00981A"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1039\/b816700c"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527619573"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200300628"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr020024j"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar900153r"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr100376w"},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201101460"},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201108001"},{"key":"e_1_2_7_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar4002069"},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.202200085"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c07126"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.4c04956"},{"key":"e_1_2_7_46_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.202300076"},{"key":"e_1_2_7_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00064a006"},{"key":"e_1_2_7_48_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201707183"},{"key":"e_1_2_7_49_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b07418"},{"key":"e_1_2_7_50_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.0c05225"},{"key":"e_1_2_7_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c02851"},{"key":"e_1_2_7_52_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4QO00208C"},{"key":"e_1_2_7_53_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201509455"},{"key":"e_1_2_7_54_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201806238"},{"key":"e_1_2_7_55_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-020-19294-8"},{"key":"e_1_2_7_56_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202009460"},{"key":"e_1_2_7_57_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2QO01676A"},{"key":"e_1_2_7_58_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)85593-3"},{"key":"e_1_2_7_59_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja901528b"},{"key":"e_1_2_7_60_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo302253c"},{"key":"e_1_2_7_61_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b09844"},{"key":"e_1_2_7_62_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201101338"},{"key":"e_1_2_7_63_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.201200065"},{"key":"e_1_2_7_64_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c06906"},{"key":"e_1_2_7_65_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)87378-6"},{"key":"e_1_2_7_66_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)82123-1"},{"key":"e_1_2_7_67_1","doi-asserted-by":"publisher","DOI":"10.1039\/D4CC03364G"},{"key":"e_1_2_7_68_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(98)00126-4"},{"key":"e_1_2_7_69_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2014.07.029"},{"key":"e_1_2_7_70_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6CS00573J"},{"key":"e_1_2_7_71_1","unstructured":"For detailed discussion see the Supporting Information."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202517136","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.202517136","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202517136","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T16:07:00Z","timestamp":1790698020000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202517136"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,10,7]]},"references-count":71,"journal-issue":{"issue":"48","published-print":{"date-parts":[[2025,11,24]]}},"alternative-id":["10.1002\/anie.202517136"],"URL":"https:\/\/doi.org\/10.1002\/anie.202517136","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,10,7]]},"assertion":[{"value":"2025-08-05","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-09-23","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-10-07","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202517136"}}