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Here, we report an organocatalytic remote C(sp<jats:sup>3<\/jats:sup>)\u2212H acylation of amides and cascade cyclization through a radical\u2010mediated 1,5\u2010hydrogen atom transfer mechanism using N\u2010heterocyclic carbene as the catalyst. Notably, a diversity of nitrogen\u2010containing substrates, including simple linear aliphatic carbamates and <jats:italic>ortho<\/jats:italic>\u2010alkyl benzamides, can be successfully applied to this organocatalytic system. With the established protocol, over 120 examples of functionalized \u03b4\u2010amino ketones and isoquinolinones with diverse substituents were easily synthesized in up to 99\u2009% yield under mild conditions. The robustness and generality of the organocatalytic strategy were further highlighted by the successful acylation of unactivated C(sp<jats:sup>3<\/jats:sup>)\u2212H bonds and late\u2010stage modification of pharmaceutical molecules. Then, the asymmetric control of the radical reaction was attempted and proven feasible by using a newly designed chiral thiazolium catalyst, and moderate enantioselectivity was obtained at the current stage. Preliminary mechanistic investigations including several control reactions, KIE experiments, and computational studies shed light on the organocatalytic radical reaction mechanism.<\/jats:p>","DOI":"10.1002\/anie.202116629","type":"journal-article","created":{"date-parts":[[2022,2,3]],"date-time":"2022-02-03T03:08:46Z","timestamp":1643857726000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":89,"title":["Remote C(sp<sup>3<\/sup>)\u2212H Acylation of Amides and Cascade Cyclization via N\u2010Heterocyclic Carbene Organocatalysis"],"prefix":"10.1002","volume":"61","author":[{"given":"Qing\u2010Zhu","family":"Li","sequence":"first","affiliation":[{"name":"Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province Sichuan Industrial Institute of Antibiotics, School of Pharmacy Chengdu University  Chengdu 610106 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rong","family":"Zeng","sequence":"additional","affiliation":[{"name":"Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province Sichuan Industrial Institute of Antibiotics, School of Pharmacy Chengdu University  Chengdu 610106 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yang","family":"Fan","sequence":"additional","affiliation":[{"name":"Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province Sichuan Industrial Institute of Antibiotics, School of Pharmacy Chengdu University  Chengdu 610106 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yan\u2010Qing","family":"Liu","sequence":"additional","affiliation":[{"name":"Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province Sichuan Industrial Institute of Antibiotics, School of Pharmacy Chengdu University  Chengdu 610106 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ting","family":"Qi","sequence":"additional","affiliation":[{"name":"Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province Sichuan Industrial Institute of Antibiotics, School of Pharmacy Chengdu University  Chengdu 610106 China"},{"name":"College of Chemical Engineering Sichuan University  Chengdu 610065 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiang","family":"Zhang","sequence":"additional","affiliation":[{"name":"Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province Sichuan Industrial Institute of Antibiotics, School of Pharmacy Chengdu University  Chengdu 610106 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4700-0142","authenticated-orcid":false,"given":"Jun\u2010Long","family":"Li","sequence":"additional","affiliation":[{"name":"Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province Sichuan Industrial Institute of Antibiotics, School of Pharmacy Chengdu University  Chengdu 610106 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,2,15]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"For selected comprehensive reviews on C\u2212H activation see:"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1038\/417507a"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1114731"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1038\/446391a"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.1607"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201810970"},{"key":"e_1_2_7_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201810970"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2020.08.017"},{"key":"e_1_2_7_8_1","unstructured":"\u00a0"},{"key":"e_1_2_7_9_2","volume-title":"The Logic of Chemical Synthesis","author":"Corey E. 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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_7_121_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201107334"},{"key":"e_1_2_7_121_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201107334"},{"key":"e_1_2_7_122_1","unstructured":"\u00a0"},{"key":"e_1_2_7_123_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202105354"},{"key":"e_1_2_7_123_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202105354"},{"key":"e_1_2_7_124_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b11824"},{"key":"e_1_2_7_125_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5SC02186C"},{"key":"e_1_2_7_126_1","unstructured":"\u00a0"},{"key":"e_1_2_7_127_2","doi-asserted-by":"publisher","DOI":"10.1007\/s00214-007-0310-x"},{"key":"e_1_2_7_128_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar700111a"},{"key":"e_1_2_7_129_1","unstructured":"Relative Gibbs free energies (\u0394G kcal\u2009mol\u22121) are relative to Breslow intermediate1IIand substrate1\u2009aat the PCM-SMD(acetonitrile)-(U)M06-2X\/6-311+G(d p)\/\/PCM-SMD(acetonitrile)-(U)M06-2X\/6-31G(d) level. Selected distances shown are in \u00c5. The superscript prefixes \u201c1\u201d \u201c2\u201d \u201c3\u201d and \u201cOS\u201d will be used to indicate the singlet doublet triplet and open-shell singlet states respectively. Other DFT-optimized geometries are provided in Figure\u2005S1 in the Supporting Information."},{"key":"e_1_2_7_130_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar50095a001"},{"key":"e_1_2_7_131_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.22885"},{"key":"e_1_2_7_132_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202111988"},{"key":"e_1_2_7_132_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202111988"},{"key":"e_1_2_7_133_1","unstructured":"\u00a0"},{"key":"e_1_2_7_134_2","unstructured":"Frontier molecular orbital (FMO) analysis (the orbital contour value is 0.03) for singlet state1COMcomplex. HOMO and LUMO represent frontier molecular orbital highest occupied molecular orbital and lowest unoccupied molecular orbital respectively."},{"key":"e_1_2_7_135_2","unstructured":"Single electron spin density (SESD) of triplet state3COMcomplex (the isosurface value is 0.006\u2005au)."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202116629","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.202116629","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202116629","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,8,23]],"date-time":"2023-08-23T06:14:14Z","timestamp":1692771254000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202116629"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,2,15]]},"references-count":168,"journal-issue":{"issue":"15","published-print":{"date-parts":[[2022,4,4]]}},"alternative-id":["10.1002\/anie.202116629"],"URL":"https:\/\/doi.org\/10.1002\/anie.202116629","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,2,15]]},"assertion":[{"value":"2021-12-06","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2022-02-15","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202116629"}}