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Nonetheless, achieving selective C\u2500H bond carboxylation of alkenes with broad applicability has long been a challenging task. Herein, we present a straightforward and unifying approach for the preparation of \u03b1\u2010carboxylic acids through nickel\u2010catalyzed radical hydrocarboxylation of both functionalized and unactivated, simple alkenes, at proximal and remote sites. Notably, this operationally simple catalytic reaction exhibits a broad substrate scope, having excellent regio\u2010 and chemoselectivities, and is suitable for late\u2010stage carboxylation of bioactive molecules. Preliminary mechanistic investigations showed that a nickel\u2010catalyzed hydrogen atom transfer (Ni\u2010HAT) pathway is in operation, accounting for the site\u2010selective hydrocarboxylation protocol for various alkene substrates.<\/jats:p>","DOI":"10.1002\/anie.202424790","type":"journal-article","created":{"date-parts":[[2025,3,20]],"date-time":"2025-03-20T07:39:03Z","timestamp":1742456343000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Proximal and Remote Hydrocarboxylation of Alkenes with Carbon Dioxide Enabled by Nickel\u2010Catalyzed Hydrogen Atom Transfer"],"prefix":"10.1002","volume":"64","author":[{"given":"Rong\u2010De","family":"He","sequence":"first","affiliation":[{"name":"Department of Chemistry National University of Singapore  Singapore 117543 Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yixin","family":"Lu","sequence":"additional","affiliation":[{"name":"Department of Chemistry National University of Singapore  Singapore 117543 Singapore"},{"name":"Energy and Environmental Nanotech Platform National University of Singapore (Suzhou) Research Institute  No.377 Linquan Street, Suzhou Industrial Park Suzhou Jiangsu 215123 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,4,3]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527693931"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-0-387-49785-3_20"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200704782"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202112835"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms6933"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2021.10.016"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/c0cs00129e"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-021-00594-1"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-022-00841-z"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c12294"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c07562"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c03671"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1007\/s41061-016-0045-z"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2018.07.011"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.1c00480"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja8062925"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja3045053"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.20150043"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature22316"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b07637"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b13448"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c05217"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.6b00334"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.8b00337"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC04112B"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CS00423C"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00388a051"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00236a014"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1246\/cl.1989.515"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1246\/cl.1989.1071"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b02844"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja4117632"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature14006"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b06458"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja507295u"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b03509"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202319515"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.2c06404"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.4c02211"},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b13757"},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.0c03884"},{"key":"e_1_2_7_42_1","first-page":"11418","volume":"146","author":"Chen F.","year":"2024","journal-title":"J. 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