{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,4]],"date-time":"2026-10-04T22:12:09Z","timestamp":1791151929637,"version":"4.1.0"},"reference-count":90,"publisher":"Wiley","issue":"25","license":[{"start":{"date-parts":[[2026,5,1]],"date-time":"2026-05-01T00:00:00Z","timestamp":1777593600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,5,1]],"date-time":"2026-05-01T00:00:00Z","timestamp":1777593600000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100003399","name":"Science and Technology Commission of Shanghai Municipality","doi-asserted-by":"publisher","award":["23YF1426700"],"award-info":[{"award-number":["23YF1426700"]}],"id":[{"id":"10.13039\/501100003399","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":[[2026,6,15]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    The conversion of amides to ketones via C(O)\u2212N bond cleavage has attracted significant attention, with cross\u2010electrophile coupling (XEC) between amides and organic halides emerging as a particularly valuable strategy. However, such transformations have so far been limited to activated amides and transition metal catalysis. The cross\u2010electrophile coupling acylation of simple\n                    <jats:italic>N<\/jats:italic>\n                    ,\n                    <jats:italic>N<\/jats:italic>\n                    \u2010dimethylamides via C(O)\u2212N bond cleavage remains challenging due to their higher chemical inertness and lower electrophilicity compared to activated amides. Herein, we report the successful development of an electroreductive cross\u2010electrophile coupling (eXEC) reaction between\n                    <jats:italic>N<\/jats:italic>\n                    ,\n                    <jats:italic>N<\/jats:italic>\n                    \u2010dimethylamides and organic halides, which affords ketones through the highly inert C(O)\u2212N bond cleavage. This work establishes an unprecedented electrochemical reduction method for C(O)\u2212N bond cleavage of\n                    <jats:italic>N,N<\/jats:italic>\n                    \u2010dimethylamides by single\u2010electron activation. Extensive experimental and computational studies elucidate the detailed reaction mechanism. The process begins with the single\u2010electron reduction of the\n                    <jats:italic>N<\/jats:italic>\n                    ,\n                    <jats:italic>N<\/jats:italic>\n                    \u2010dimethylamide in a lithium\u2010ion electroreduction system, generating a ketyl radical anion. This key intermediate disrupts the amide resonance, weakening the C(O)\u2212N bond. Consequently, this facilitates the typically challenging radical\u2010radical cross\u2010coupling, followed by scission of the C(O)\u2212N bond. The observed selectivity of the cross\u2010coupling is governed by the combined effects of a thermodynamic preference for coupling and the high concentration disparity between the two distinct radical species.\n                  <\/jats:p>","DOI":"10.1002\/anie.8873247","type":"journal-article","created":{"date-parts":[[2026,5,1]],"date-time":"2026-05-01T08:03:39Z","timestamp":1777622619000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Electroreductive Radical C\u2013C Acylation Coupling from\n                    <i>N<\/i>\n                    ,\n                    <i>N<\/i>\n                    \u2010Dimethylamides and Organic Halides via Inert C(O)\u2212N Bond Cleavage: Facile Access to Aryl Ketones"],"prefix":"10.1002","volume":"65","author":[{"given":"Lu","family":"Chen","sequence":"first","affiliation":[{"name":"Precise Synthesis and Function Development Key Laboratory of Sichuan Province College of Chemistry and Chemical Engineering China West Normal University  Nanchong China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6424-4491","authenticated-orcid":false,"given":"Lin\u2010Hai","family":"Jing","sequence":"additional","affiliation":[{"name":"Precise Synthesis and Function Development Key Laboratory of Sichuan Province College of Chemistry and Chemical Engineering China West Normal University  Nanchong China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yong\u2010Qi","family":"Huang","sequence":"additional","affiliation":[{"name":"Precise Synthesis and Function Development Key Laboratory of Sichuan Province College of Chemistry and Chemical Engineering China West Normal University  Nanchong China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pan","family":"Han","sequence":"additional","affiliation":[{"name":"Precise Synthesis and Function Development Key Laboratory of Sichuan Province College of Chemistry and Chemical Engineering China West Normal University  Nanchong China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuan\u2010Yuan","family":"Liu","sequence":"additional","affiliation":[{"name":"Precise Synthesis and Function Development Key Laboratory of Sichuan Province College of Chemistry and Chemical Engineering China West Normal University  Nanchong China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7930-2324","authenticated-orcid":false,"given":"Chong\u2010Lei","family":"Ji","sequence":"additional","affiliation":[{"name":"School of Physical Science and Technology ShanghaiTech University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7458-4465","authenticated-orcid":false,"given":"Zheng\u2010Bing","family":"Zhang","sequence":"additional","affiliation":[{"name":"Precise Synthesis and Function Development Key Laboratory of Sichuan Province College of Chemistry and Chemical Engineering China West Normal University  Nanchong China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,5,1]]},"reference":[{"key":"e_1_2_7_2_1","volume-title":"The Amide Linkage: Selected Structural Aspects in Chemistry, Biochemistry, and Materials Science","author":"Greenberg A.","year":"2000"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.6b00486"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2011.08.031"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201207306"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00029a005"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar990008h"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202102805"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/jr9550003334"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1055\/s\u20101984\u201030782"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00369a002"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC03927A"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.1268"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/ajoc.201200066"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2015.04.074"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1038\/s42004\u2010021\u201000575\u20102"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010020\u201016948\u20105"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.8b00410"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b03277"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201605012"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201800109"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms14993"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.2c01094"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CS00335A"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.trechm.2020.08.001"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/tcr.201900072"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.1c00225"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202004441"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.2c01094"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040\u20104039(01)91316\u20104"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1055\/s\u20100028\u20101083226"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.8b02815"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.7b03688"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.2388"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201703174"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b06191"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.4c00103"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.1c05738"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.1c01535"},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b02323"},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.8b02911"},{"key":"e_1_2_7_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.8b01021"},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.7b02288"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.0c00485"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.7b00373"},{"key":"e_1_2_7_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.8b03901"},{"key":"e_1_2_7_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b00793"},{"key":"e_1_2_7_48_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b09482"},{"key":"e_1_2_7_49_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.5b02209"},{"key":"e_1_2_7_50_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201602202"},{"key":"e_1_2_7_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.9b04497"},{"key":"e_1_2_7_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.9b05159"},{"key":"e_1_2_7_53_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202114146"},{"key":"e_1_2_7_54_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1QO00944C"},{"key":"e_1_2_7_55_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201200271"},{"key":"e_1_2_7_56_1","doi-asserted-by":"publisher","DOI":"10.1002\/1521\u20103773(20020902)41:17<3188::AID\u2010ANIE3188>3.0.CO;2\u2010H"},{"key":"e_1_2_7_57_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201502894"},{"key":"e_1_2_7_58_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b00842"},{"key":"e_1_2_7_59_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527830251.ch13"},{"key":"e_1_2_7_60_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.8b01380"},{"key":"e_1_2_7_61_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.0c00442"},{"key":"e_1_2_7_62_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.2c03268"},{"key":"e_1_2_7_63_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.7b00831"},{"key":"e_1_2_7_64_1","unstructured":"The C(O)\u2013N bond resonance energy ofN N\u2010dimethylamide is greater than 16\u00a0kcal\/mol and the reported C(O)\u2013N bond resonance energy of actived amides is 11\u201014\u00a0kcal\/mol (see reference 17)."},{"key":"e_1_2_7_65_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b03616"},{"key":"e_1_2_7_66_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00386"},{"key":"e_1_2_7_67_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC01402K"},{"key":"e_1_2_7_68_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.1c00384"},{"key":"e_1_2_7_69_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201711060"},{"key":"e_1_2_7_70_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CS00223F"},{"key":"e_1_2_7_71_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00397"},{"key":"e_1_2_7_72_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c08008"},{"key":"e_1_2_7_73_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202211952"},{"key":"e_1_2_7_74_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.esci.2022.04.006"},{"key":"e_1_2_7_75_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202306679"},{"key":"e_1_2_7_76_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.1c00148"},{"key":"e_1_2_7_77_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.aav5606"},{"key":"e_1_2_7_78_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b12112"},{"key":"e_1_2_7_79_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41586\u2010022\u201004540\u20104"},{"key":"e_1_2_7_80_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c12071"},{"key":"e_1_2_7_81_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c06794"},{"key":"e_1_2_7_82_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201903726"},{"key":"e_1_2_7_83_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202115497"},{"key":"e_1_2_7_84_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.1c00931"},{"key":"e_1_2_7_85_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201803539"},{"key":"e_1_2_7_86_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00977a061"},{"key":"e_1_2_7_87_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01043a029"},{"key":"e_1_2_7_88_1","unstructured":"The calculated result indicated that formation of acyl radical through direct C(O)\u2212N bond cleavage ofN N\u2010dimethylbenzamide or a ketyl radical anion is energetically unfavorable (see Supporting Information)."},{"key":"e_1_2_7_89_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202203694"},{"key":"e_1_2_7_90_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202210201"},{"key":"e_1_2_7_91_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacsau.3c00305"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.8873247","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.8873247","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.8873247","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,6,15]],"date-time":"2026-06-15T09:52:07Z","timestamp":1781517127000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.8873247"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,5,1]]},"references-count":90,"journal-issue":{"issue":"25","published-print":{"date-parts":[[2026,6,15]]}},"alternative-id":["10.1002\/anie.8873247"],"URL":"https:\/\/doi.org\/10.1002\/anie.8873247","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,5,1]]},"assertion":[{"value":"2026-02-08","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-04-15","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-05-01","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e8873247"}}