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The calculations provide a detailed mechanistic comparison of the experimentally observed reaction pathways and reveal distinct downstream reactivity of the corresponding radical intermediates. Activation strain model (ASM) analyses show that the competing cyclization and C\u2013C bond cleavage via \u03b2-scission pathways are characterized by different balances between structural distortion and interfragment interactions. For the cyanomethyl-radical-derived system, the cyclization pathway is associated with a substantially lower distortion energy, whereas for the \u03b1-oxyalkyl-radical-derived system, the cleavage pathway benefits from stronger stabilizing interfragment interactions that compensate for the larger distortion penalty. Noncovalent interaction (NCI) analyses provide qualitative structural support for these energetic trends. Overall, these computations provide a detailed mechanistic comparison of the competing downstream pathways of the cyanomethyl- and \u03b1-oxyalkyl-radical-derived intermediates.<\/jats:p>","DOI":"10.1021\/acs.joc.6c01863","type":"journal-article","created":{"date-parts":[[2026,10,20]],"date-time":"2026-10-20T00:01:22Z","timestamp":1792454482000},"page":"14423-14430","source":"Crossref","is-referenced-by-count":0,"title":["Deciphering the Mechanistic Origin of Divergent Radical Annulation Reactions of\n                    <i>ortho<\/i>\n                    -Cyanoaryl Acrylamides"],"prefix":"10.1021","volume":"91","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7113-2551","authenticated-orcid":true,"given":"Meryem","family":"F\u0131st\u0131k\u00e7\u0131","sequence":"first","affiliation":[{"name":"Vocational School of Health Services, Hakkari University , , ,","place":["Hakkari, T\u00fcrkiye, 30000"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6742-0443","authenticated-orcid":true,"given":"Yunus","family":"Zozik","sequence":"additional","affiliation":[{"name":"Oltu Vocational School, Atat\u00fcrk University , , Oltu , ,","place":["Erzurum, T\u00fcrkiye, 25400"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2850-4361","authenticated-orcid":true,"given":"Sel\u00e7uk","family":"E\u015fsiz","sequence":"additional","affiliation":[{"name":"Vocational School of Health Services, Hakkari University , , ,","place":["Hakkari, T\u00fcrkiye, 30000"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,19]]},"reference":[{"key":"2026103005070087000_cit1a","doi-asserted-by":"publisher","first-page":"4626","DOI":"10.1039\/c8cs00947c","article-title":"Catalytic Cascade Reactions by Radical Relay","volume":"48","author":"Huang","year":"2019","journal-title":"Chem. 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