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Therefore, exploring efficient and sustainable methodologies for their synthesis is indispensable. Herein, we disclose an alternative and greener method for synthesizing an unexplored new class of amidines through the photochemical synergistic effect of copper\/nitroxyl radical catalysis. This approach facilitates site\u2010selective radical amination of unactivated imine C(sp<jats:sup>2<\/jats:sup>)\u2212H bond in <jats:italic>C,N,N<\/jats:italic>\u2010cyclic imines over favored selectivity <jats:italic>via<\/jats:italic> halogen\u2010atom transfer (XAT). This greener method ticks 11 out of 12 green chemistry metrics (GCM), effectively sidestepping the need for oxidants, bases, ligands, multistep processes, and harsh conditions, distinguishing it from conventional methods described in previous studies. Kinetic, spectroscopic, and computational tools have been employed to elucidate the synergistic effect of Cu\/nitroxyl radical, the role of light, XAT, the influence of substituents, and the order of the reaction in the catalytic cycle.<\/jats:p>","DOI":"10.1002\/chem.202404599","type":"journal-article","created":{"date-parts":[[2025,1,24]],"date-time":"2025-01-24T03:28:35Z","timestamp":1737689315000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Alternative and Sustainable Route to Explore a New Class of Amidines by Photochemical Synergistic Effect of Copper\/Nitroxyl Radical Catalysis <i>via<\/i> Halogen\u2010Atom Transfer"],"prefix":"10.1002","volume":"31","author":[{"given":"Chandrasekaran","family":"Sivaraj","sequence":"first","affiliation":[{"name":"Department of Chemistry Vellore Institute of Technology  Vellore 632014 Tamil Nadu India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0461-5155","authenticated-orcid":false,"given":"Thirumanavelan","family":"Gandhi","sequence":"additional","affiliation":[{"name":"Department of Chemistry Vellore Institute of Technology  Vellore 632014 Tamil Nadu India"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,2,10]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","first-page":"2947","volume":"3","author":"Arora P.","year":"2012","journal-title":"Ijpsr"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.7897\/2230-8407.04615"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6OB00936K"},{"key":"e_1_2_7_5_2","first-page":"141","volume":"9","author":"Al-Mulla A. 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