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However, unlike most contemporary radical\u2010generating mechanisms, the direct excitation to homolyze chemical bonds and produce aliphatic carbon\u2010centered radicals under visible light remains rare, especially in metallaphotoredox cross couplings. Herein, we present our design of the dihydropyrimidoquinolinone (DHPQ) reagents derived from ketones, which can undergo formal deacylation and homolytic C\u2212C bond cleavage to release alkyl radicals without external photocatalysts. Spectroscopic and computational analysis reveal unique optical and structural features of DHPQs, rationalizing their faster kinetics in alkyl radical generation than a structurally similar but visible\u2010light transparent radical precursor. Such a capability allows DHPQ to facilitate a wide range of Ni\u2010metallaphotoredox cross couplings with aryl, alkynyl and acyl halides. Other catalytic and non\u2010catalyzed alkylative transformations of DHPQs are also feasible with various radical acceptors. We believe this work would be of broad interest, aiding the synthetic planning with simplified operation and expanding the synthetic reach of photocatalyst\u2010free approaches in cutting\u2010edge research.<\/jats:p>","DOI":"10.1002\/anie.202410363","type":"journal-article","created":{"date-parts":[[2024,7,24]],"date-time":"2024-07-24T01:56:10Z","timestamp":1721786170000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":29,"title":["Direct Excitation Strategy for Deacylative Couplings of Ketones"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4956-7625","authenticated-orcid":false,"given":"Jianbin","family":"Li","sequence":"first","affiliation":[{"name":"School of Science and Engineering The Chinese University of Hong Kong, Shenzhen  2001 Longxiang Road, Longgang District Shenzhen, Guangdong 518172 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ding","family":"Zhang","sequence":"additional","affiliation":[{"name":"School of Science and Engineering The Chinese University of Hong Kong, Shenzhen  2001 Longxiang Road, Longgang District Shenzhen, Guangdong 518172 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lida","family":"Tan","sequence":"additional","affiliation":[{"name":"Department of Chemistry McGill University  801 Sherbrooke St. West Montr\u00e9al, Qu\u00e9bec H3\u2005A 0B8 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3859-8824","authenticated-orcid":false,"given":"Chao\u2010Jun","family":"Li","sequence":"additional","affiliation":[{"name":"Department of Chemistry McGill University  801 Sherbrooke St. West Montr\u00e9al, Qu\u00e9bec H3\u2005A 0B8 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,9,12]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.6b00214"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.6b00351"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41570-017-0052"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201809431"},{"key":"e_1_2_8_5_1","first-page":"471","volume-title":"Organic Reactions, Vol. 100","author":"Nacsa E. 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