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High selectivity directly minimizes undesired by\u2010products, thereby increasing the atom economy and eliminating the wasteful purification steps. While the control of chemoselectivity is precisely achieved by the reactivity variation between two different functional groups, that of site\u2010selectivity is a challenging task. Historically, substrate\u2010directed approaches have played a key role in realizing site\u2010selective transformations. On contrary, modern site\u2010selective approaches are rather dependent on radical chemistry. In this context, transformations via metal\u2010catalyzed SET\u2010induced formation of radical intermediates arguably represent a powerful strategy that has received considerable attention within last two decades. Among the various classes, a radical intermediate adjacent to a C\n                    <jats:sub>sp<\/jats:sub>\n                    <jats:sup>2<\/jats:sup>\n                    center is relatively stabilized compared to the corresponding alkyl radical species, which is attributed to the resonance delocalization of the unpaired electron into the adjacent system. By engaging those radical intermediates, numerous approaches that have been accomplished proceed with amazingly perfect chemo\u2010 and site\u2010selectivity. Noteworthy instances include transformations via the formation of carboxylate radicals and \u03b1\u2010carbonyl radicals from carboxylic acids, ketones, etc. In this account, we describe developments on this area that have emanated primarily from our original research together with a few instances of closely related works by others.\n                  <\/jats:p>","DOI":"10.1002\/tcr.70231","type":"journal-article","created":{"date-parts":[[2026,8,24]],"date-time":"2026-08-24T09:50:07Z","timestamp":1787565007000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Controlling Chemo\u2010 and Site\u2010Selectivity Through the Formation of Radicals Adjacent to a sp\n                    <sup>2<\/sup>\n                    Carbon"],"prefix":"10.1002","author":[{"given":"Anil Rajendra","family":"Paraskar","sequence":"first","affiliation":[{"name":"Inorganic Materials and Catalysis Division CSIR\u2010Central Salt and Marine Chemicals Research Institute  Bhavnagar India"},{"name":"Academy of Scientific and Innovative Research (AcSIR)  Ghaziabad India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rupali Dasharath","family":"Shinde","sequence":"additional","affiliation":[{"name":"Inorganic Materials and Catalysis Division CSIR\u2010Central Salt and Marine Chemicals Research Institute  Bhavnagar India"},{"name":"Academy of Scientific and Innovative Research (AcSIR)  Ghaziabad India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1266-0930","authenticated-orcid":false,"given":"Sukalyan","family":"Bhadra","sequence":"additional","affiliation":[{"name":"Inorganic Materials and Catalysis Division CSIR\u2010Central Salt and Marine Chemicals Research Institute  Bhavnagar India"},{"name":"Academy of Scientific and Innovative Research (AcSIR)  Ghaziabad India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,8,24]]},"reference":[{"key":"e_1_2_11_2_1","doi-asserted-by":"crossref","first-page":"1077","DOI":"10.1351\/pac199466051077","article-title":"Glossary of Terms Used in Physical Organic Chemistry, Pure","volume":"66","author":"Muller P.","year":"1994","journal-title":"Pure and Applied Chemistry"},{"key":"e_1_2_11_3_1","volume-title":"Advanced Organic Chemistry: Reactions, Mechanisms, and Structure","author":"March J.","year":"1992"},{"key":"e_1_2_11_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.6b00476"},{"key":"e_1_2_11_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.7b03180"},{"key":"e_1_2_11_6_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7CC00368D"},{"key":"e_1_2_11_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00514"},{"key":"e_1_2_11_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/tcr.202000132"},{"key":"e_1_2_11_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/D4SC06777K"},{"key":"e_1_2_11_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5c07456"},{"key":"e_1_2_11_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/B607547A"},{"key":"e_1_2_11_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201609105"},{"key":"e_1_2_11_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.7b00148"},{"key":"e_1_2_11_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201814457"},{"key":"e_1_2_11_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202009995"},{"key":"e_1_2_11_16_1","doi-asserted-by":"crossref","first-page":"561","DOI":"10.1055\/a-1904-0420","article-title":"Functionalization of Alkyl Groups Adjacent to Azoles: Application to the Synthesis of \u03b1\u2010Functionalized Carboxylic Acids","volume":"34","author":"Singh A. 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