{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,31]],"date-time":"2026-10-31T00:36:05Z","timestamp":1793406965620,"version":"4.5.0"},"reference-count":50,"publisher":"American Chemical Society (ACS)","issue":"7","license":[{"start":{"date-parts":[[2026,7,7]],"date-time":"2026-07-07T00:00:00Z","timestamp":1783382400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001501","name":"University Grants Commission","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100001501","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001843","name":"Science and Engineering Research Board","doi-asserted-by":"publisher","award":["ANRF\/ARG\/2025\/012163\/CS"],"award-info":[{"award-number":["ANRF\/ARG\/2025\/012163\/CS"]}],"id":[{"id":"10.13039\/501100001843","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100004541","name":"Ministry of Education, India","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100004541","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,7,27]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The use of formate salt as a C1 synthon offers a practical and accessible carboxylating reagent relative to the gaseous alternatives. However, photochemical transient CO2\u2022\u2013 generation from formate and its utilization for carboxylation reactions is mostly restricted to the activated alkenes. Herein, we report a general, photocatalytic platform for the selective anti-Markovnikov hydrocarboxylation of unactivated and activated alkenes using formate salt. The scope of the protocol is demonstrated through the selective hydrocarboxylation of a range of alkenes, independent of the chain length. The control experiments and preliminary mechanistic studies indicate synergy between the tertiary aminium radical cation-mediated hydrogen atom abstraction (HAA) and efficient hydrogen atom transfer (HAT) from the silyl hydride underpin the controlled hydrocarboxylation process. Mechanistic studies also indicate that the radical-polar crossover of the carboxylated alkyl radical can be avoided by the judicious choice of the HAT reagent, providing access to unactivated alkenes in the hydrocarboxylation reaction utilizing formate. This strategy using light energy is mild, robust, and effective for the carboxylation of various alkenes under ambient conditions. Our method enables a modular route for the controlled, steady-state release of CO2\u2022\u2013 using formate, providing a unique pathway for the carboxylation of organic molecules. The application of this protocol has been demonstrated through the large-scale synthesis, synthetic manipulation, and synthesis of isotopically labeled aliphatic carboxylic acids from unactivated and activated alkenes.<\/jats:p>","DOI":"10.1021\/jacsau.6c00527","type":"journal-article","created":{"date-parts":[[2026,7,7]],"date-time":"2026-07-07T23:39:17Z","timestamp":1783467557000},"page":"4004-4013","source":"Crossref","is-referenced-by-count":1,"title":["Photocatalytic, Scalable\nAnti-Markovnikov Hydrocarboxylation\nof Unactivated Alkenes via Amine-Mediated CO2\u2022\u2013 Generation from Formate"],"prefix":"10.1021","volume":"6","author":[{"given":"Pintu","family":"Ghosh","sequence":"first","affiliation":[{"name":"Indian Institute of Technology Bombay , , Powai , ,","place":["Mumbai, India, 400076"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bikiran","family":"Pal","sequence":"additional","affiliation":[{"name":"Indian Institute of Technology Bombay , , Powai , ,","place":["Mumbai, India, 400076"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8353-1306","authenticated-orcid":true,"given":"Debabrata","family":"Maiti","sequence":"additional","affiliation":[{"name":"Indian Institute of Technology Bombay , , Powai , ,","place":["Mumbai, India, 400076"]},{"name":"Indian Institute of Technology Bombay , , Powai , ,","place":["Mumbai, India, 400076"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,7]]},"reference":[{"key":"2026072709065774800_cit1","doi-asserted-by":"crossref","DOI":"10.1007\/978-0-387-49785-3_20","volume-title":"Prodrugs of Carboxylic\nAcids","author":"Maag","year":"2007"},{"key":"2026072709065774800_cit2","doi-asserted-by":"publisher","first-page":"3100","DOI":"10.1002\/anie.200704782","article-title":"Carboxylic Acids as Substrates in\nHomogeneous Catalysis","volume":"47","author":"Goo\u00dfen","year":"2008","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026072709065774800_cit3","doi-asserted-by":"publisher","first-page":"3167","DOI":"10.1039\/D4SU00482E","article-title":"Carboxylation reactions\nfor the sustainable\nmanufacture of chemicals and monomers","volume":"2","author":"Faba","year":"2024","journal-title":"RSC Sustainability"},{"key":"2026072709065774800_cit4","doi-asserted-by":"publisher","first-page":"3098","DOI":"10.1039\/c7cc00678k","article-title":"Construction\nof a visible light-driven hydrocarboxylation cycle of alkenes by the\ncombined use of Rh(i) and photoredox catalysts","volume":"53","author":"Murata","year":"2017","journal-title":"Chem. Commun."},{"key":"2026072709065774800_cit5","doi-asserted-by":"publisher","first-page":"6726","DOI":"10.1039\/D5CS00181A","article-title":"Navigating\nthe functionalization of unactivated alkenes via visible light photocatalysis","volume":"54","author":"Cao","year":"2025","journal-title":"Chem. Soc. Rev."},{"key":"2026072709065774800_cit6","doi-asserted-by":"publisher","first-page":"100525","DOI":"10.1016\/j.cogsc.2021.100525","article-title":"Recent\nprogress and challenges in carboxylation with CO2","volume":"32","author":"Ran","year":"2021","journal-title":"Curr. Opin. Green Sust."},{"key":"2026072709065774800_cit7","doi-asserted-by":"publisher","first-page":"2728","DOI":"10.1021\/acs.accounts.4c00417","article-title":"Recent\nAdvances in Electrochemical Carboxylation with CO2","volume":"57","author":"Sun","year":"2024","journal-title":"Acc. Chem. Res."},{"key":"2026072709065774800_cit8","doi-asserted-by":"publisher","first-page":"2518","DOI":"10.1021\/acs.accounts.1c00135","article-title":"Radical Carboxylative\nCyclizations and Carboxylations with CO2","volume":"54","author":"Ye","year":"2021","journal-title":"Acc. Chem. Res."},{"key":"2026072709065774800_cit9","doi-asserted-by":"publisher","first-page":"439","DOI":"10.1016\/j.ccr.2018.07.011","article-title":"Transition metal-catalyzed carboxylation\nof unsaturated substrates with CO2","volume":"374","author":"Yan","year":"2018","journal-title":"Coord. Chem. Rev."},{"key":"2026072709065774800_cit10","doi-asserted-by":"publisher","first-page":"1327","DOI":"10.1055\/a-2012-5317","article-title":"Recent Advances on\nthe Carboxylations of C(sp3)\u2013H\nBonds Using CO2 as the Carbon Source","volume":"34","author":"Pradhan","year":"2023","journal-title":"Synlett"},{"key":"2026072709065774800_cit11","doi-asserted-by":"publisher","first-page":"9371","DOI":"10.1039\/D1CS00921D","article-title":"Challenges\nand recent advancements in the transformation of CO2 into\ncarboxylic acids: straightforward assembly with homogeneous 3d metals","volume":"51","author":"Cauwenbergh","year":"2022","journal-title":"Chem. Soc. 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Soc."},{"key":"2026072709065774800_cit34","doi-asserted-by":"publisher","first-page":"6100","DOI":"10.1039\/D2GC01256A","article-title":"Visible-light-driven\nregioselective carbocarboxylation of 1,3-dienes with organic halides\nand CO2","volume":"24","author":"Zhou","year":"2022","journal-title":"Green Chem."},{"key":"2026072709065774800_cit35","doi-asserted-by":"publisher","first-page":"2149","DOI":"10.1021\/acscatal.2c06377","article-title":"Dicarboxylation of Alkenes with CO2 and Formate via\nPhotoredox Catalysis","volume":"13","author":"Xu","year":"2023","journal-title":"ACS Catal."},{"key":"2026072709065774800_cit36","doi-asserted-by":"publisher","first-page":"9750","DOI":"10.1021\/acs.joc.3c02887","article-title":"\u03b1-Amino\nAcids by Reductive Carboxylation of Imines. Using Formate and CO2","volume":"89","author":"Xu","year":"2024","journal-title":"J. Org. Chem."},{"key":"2026072709065774800_cit37","doi-asserted-by":"publisher","first-page":"8987","DOI":"10.1021\/jacs.1c04427","article-title":"Radical\nChain Reduction via Carbon Dioxide Radical Anion (CO2\u2022\u2013)","volume":"143","author":"Hendy","year":"2021","journal-title":"J. Am. Chem. Soc."},{"key":"2026072709065774800_cit38","doi-asserted-by":"publisher","first-page":"10882","DOI":"10.1021\/jacs.1c05988","article-title":"Non-innocent\nRadical Ion Intermediates in Photoredox Catalysis: Parallel Reduction\nModes Enable Coupling of Diverse Aryl Chlorides","volume":"143","author":"Chmiel","year":"2021","journal-title":"J. Am. Chem. Soc."},{"key":"2026072709065774800_cit39","doi-asserted-by":"publisher","first-page":"35035","DOI":"10.1021\/jacs.4c14421","article-title":"Alkene Carboxy-Alkylation via CO2\u2022\u2013","volume":"146","author":"Dang","year":"2024","journal-title":"J. Am. Chem. 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Sci."},{"key":"2026072709065774800_cit46","doi-asserted-by":"publisher","first-page":"10165","DOI":"10.1002\/chem.201901650","article-title":"Infrared Spectroscopy of Size-Selected\nHydrated Carbon Dioxide Radical Anions CO2.\u2013(H2O)n (n = 2\u201361) in the C\u2013O\nStretch Region","volume":"25","author":"Herburger","year":"2019","journal-title":"Chem\u2013Eur. 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