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Here, we present a redox\u2010neutral approach to address this difficulty by leveraging the synergistic interplay between photocatalysis and cascade hydrogen abstraction cycles. Remarkably, this strategy eliminates the need for sacrificial electron donors, electron acceptors, or stoichiometric additives, offering enhanced atom economy and environmental sustainability. It is particular that the combination of \u03b1\u2010amino alkyl radicals with sulfur radicals generated in\u2005situ from the decomposition of DMSO was employed to realize the abstraction of benzylic tertiary C\u2212H bonds. Our method enables the direct synthesis of a diverse array of benzylic quaternary carboxylic acids with excellent functional group tolerance as well as the derivatization of bioactive molecules and the gram\u2010scale synthesis of pharmaceuticals under mild reaction conditions.\n                  <\/jats:p>","DOI":"10.1002\/anie.202420852","type":"journal-article","created":{"date-parts":[[2024,11,27]],"date-time":"2024-11-27T10:25:56Z","timestamp":1732703156000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":21,"title":["Redox\u2010Neutral Carboxylation of Benzylic Tertiary C\u2212H Bonds with Carbon Dioxide"],"prefix":"10.1002","volume":"64","author":[{"given":"Jun\u2010Li","family":"Li","sequence":"first","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences CAS Key Laboratory of Molecular Recognition and Function Institute of Chemistry Chinese Academy of Sciences  Beijing 100190 P.\u2005R. 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Am. Chem. Soc."},{"key":"e_1_2_3_69_1","unstructured":"In order to clarify the dechlorinated process we carried out reactions with 1-chloro-4-isopropylbenzene (1\u2009k) and 2-(4-chlorophenyl)-2-methylpropanoic acid (2\u2009k) as the starting materials under N2instead of CO2 respectively. Both led to minor dechlorinated products under this reductive condition thereby explaining the generation of the dechlorinated products under CO2."},{"key":"e_1_2_3_70_1","unstructured":"We stopped the reaction at different times (4\u2005h 8\u2005h and 12\u2005h) when using 4 4\u2032-diisopropyl-1 1\u2032-biphenyl as the starting material we only observed the formation of dicarboxylic acid (2\u2009ba) indicating that the mono-carboxylic acid intermediate would react much faster than the starting material for carboxylation with CO2. Compared with benzene 1 1\u2032-biphenyl and naphthalene have increased conjugation effect. Thus benzylic radicals generated through HAT processes would be more stable for 1 1\u2032-biphenyl and naphthalene which could provide more probability for reduction to generate benzylic anions. Meanwhile these benzylic anions would also be more stabilized by 1 1\u2032-biphenyl and naphthalene than benzene to have longer lifetime to react with CO2. Therefore highly selective formation of dicarboxylic acids was observed upon substitution with 4 4\u2032-diisopropyl-1 1\u2032-biphenyl or 2 6-diisopropylnaphthalene."},{"key":"e_1_2_3_71_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0OB01884H"},{"key":"e_1_2_3_72_1","doi-asserted-by":"publisher","DOI":"10.3762\/bjoc.18.119"},{"key":"e_1_2_3_73_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201107334"},{"key":"e_1_2_3_73_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201107334"},{"key":"e_1_2_3_74_1","unstructured":"\u00a0"},{"key":"e_1_2_3_75_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202406880"},{"key":"e_1_2_3_76_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-022-35774-5"},{"key":"e_1_2_3_77_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5SC02185E"},{"key":"e_1_2_3_78_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.aba2419"},{"key":"e_1_2_3_79_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100062a009"},{"key":"e_1_2_3_80_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.oprd.1c00063"},{"key":"e_1_2_3_81_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00209a021"},{"key":"e_1_2_3_82_1","unstructured":"Consecutive photoinduced electron transfer (ConPET) is also possible to promote the generation of the benzylic anion species see:"},{"key":"e_1_2_3_83_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1258232"},{"key":"e_1_2_3_84_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c05994"},{"key":"e_1_2_3_85_1","unstructured":"\u00a0"},{"key":"e_1_2_3_86_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c12720"},{"key":"e_1_2_3_87_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c14146"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202420852","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.202420852","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202420852","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T04:01:44Z","timestamp":1790568104000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202420852"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,12,4]]},"references-count":98,"journal-issue":{"issue":"6","published-print":{"date-parts":[[2025,2,3]]}},"alternative-id":["10.1002\/anie.202420852"],"URL":"https:\/\/doi.org\/10.1002\/anie.202420852","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,12,4]]},"assertion":[{"value":"2024-10-28","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2024-12-04","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202420852"}}