{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,4]],"date-time":"2026-09-04T04:23:00Z","timestamp":1788495780588,"version":"build-2803163510"},"reference-count":68,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2023,12,20]],"date-time":"2023-12-20T00:00:00Z","timestamp":1703030400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22337005, 91753126"],"award-info":[{"award-number":["22337005, 91753126"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100012247","name":"Program of Shanghai Academic Research Leader","doi-asserted-by":"publisher","award":["21XD1424700"],"award-info":[{"award-number":["21XD1424700"]}],"id":[{"id":"10.13039\/501100012247","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":[[2024,1,22]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Boronate rearrangements, such as the Matteson and Petasis reactions, are valuable metal\u2010free reactions for the transfer of the carbo group on boron to intramolecular electrophilic sites. However, only highly reactive electrophiles are suitable, and ketones are too inactive for those boronate rearrangements due to the high energy barriers. We disclose here the 1,3\u2010boronate rearrangement to ketones, for which a high energy barrier (44.9\u2005kcal\/mol) is prohibitory for thermal reactions in the ground state. The reaction is enabled by the key keto\u2010enol\u2010boronate bidentate complex formation in situ, which absorbs visible light to reach the excited state for the chemoselective 1,3\u2010boronate rearrangement to ketones. Experimental and computational investigations exclude free radical intermediates from organoboronates. The aryl, alkenyl, and alkyl boronic acids react with various 1,3\u2010diketones driven by visible light irradiation to construct structurally diverse \u03b2\u2010keto tertiary alcohols under metal\u2010free conditions. The reaction demonstrates substrate diversity with 58 examples, yields up to 98\u2009%, and it is suitable for gram\u2010scale synthesis.<\/jats:p>","DOI":"10.1002\/anie.202316481","type":"journal-article","created":{"date-parts":[[2023,12,8]],"date-time":"2023-12-08T14:18:29Z","timestamp":1702045109000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":17,"title":["Metal\u2010Free 1,3\u2010Boronate Rearrangement to Ketones Driven by Visible Light"],"prefix":"10.1002","volume":"63","author":[{"given":"Kejia","family":"Hao","sequence":"first","affiliation":[{"name":"State Key Laboratory of Chemical Biology Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences  345 Lingling Road Shanghai 200032 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Defang","family":"Li","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Biology Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences  345 Lingling Road Shanghai 200032 China"},{"name":"School of Physical Science and Technology ShanghaiTech University  100 Haike Road Shanghai 201210 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dongmin","family":"Fu","sequence":"additional","affiliation":[{"name":"Green Catalysis Center College of Chemistry Zhengzhou University  Zhengzhou Henan 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Peng","family":"Zou","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Biology Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences  345 Lingling Road Shanghai 200032 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shasha","family":"Xie","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Biology Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences  345 Lingling Road Shanghai 200032 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yu","family":"Lan","sequence":"additional","affiliation":[{"name":"Green Catalysis Center College of Chemistry Zhengzhou University  Zhengzhou Henan 450001 China"},{"name":"School of Chemistry and Chemical Engineering Chongqing Key Laboratory of Theoretical and Computational Chemistry Chongqing University  Chongqing 400030 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0916-0994","authenticated-orcid":false,"given":"Yiyun","family":"Chen","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Biology Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences  345 Lingling Road Shanghai 200032 China"},{"name":"School of Physical Science and Technology ShanghaiTech University  100 Haike Road Shanghai 201210 China"},{"name":"School of Chemistry and Material Sciences Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences  1 Sub-lane Xiangshan Hangzhou 310024 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,12,20]]},"reference":[{"key":"e_1_2_3_1_1","unstructured":"\u00a0"},{"key":"e_1_2_3_2_2","first-page":"1","volume-title":"Structure, Properties, and Preparation of Boronic Acid Derivatives. Overview of Their Reactions and Applications. In Boronic Acids","author":"Hall D. G.","year":"2005"},{"key":"e_1_2_3_3_2","doi-asserted-by":"crossref","unstructured":"E. Fernandez A. Whiting Synthesis and Application of Organoboron Compounds Preface. InSynthesis and Application of Organoboron Compounds Vol. 49(Eds.: E. Fernandez A. Whiting) Springer Berlin 2015 pp. V\u2013VI.","DOI":"10.1007\/978-3-319-13054-5"},{"key":"e_1_2_3_4_1","unstructured":"\u00a0"},{"key":"e_1_2_3_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00039a007"},{"key":"e_1_2_3_6_2","doi-asserted-by":"crossref","unstructured":"A. de Mejiere F. Diederich Metal-Catalyzed Cross-Coupling Reactions. 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These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."},{"key":"e_1_2_3_52_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(99)00053-4"},{"key":"e_1_2_3_53_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2005.03.014"},{"key":"e_1_2_3_54_1","doi-asserted-by":"publisher","DOI":"10.1039\/J29670001295"},{"key":"e_1_2_3_55_1","unstructured":"When strict freeze\/thaw cycles are performed 1.5\u2005equiv. of aryl boronic acids are sufficient for the reaction in 85\u2009% yields in 16\u2005h. When only the nitrogen inflation is performed 1.5\u2005equiv. of boronic acids give 78\u2009% yields in 8\u2005h. See Table\u2005S12 for details."},{"key":"e_1_2_3_56_1","first-page":"1295","volume":"11","author":"Yan G.","year":"2013","journal-title":"Org. Biomol. 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