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Unlike C, O, and N linkers, systems with B, Si, P, S, Ge, As, and Se linkers are shown to favor 6\u2010endo\u2010dig cyclization. This offers fundamental insights into the rational synthetic design of cyclic compounds. A thorough analysis of stereoelectronic effects, cyclization barriers, and intrinsic barriers illustrates that structural changes alter the cyclization preference by mainly impacting 5\u2010exo\u2010dig reaction barriers. Based on the high\u2010level computational modeling, we proceed to develop a new tool for cyclization preference prediction from the correlation between cyclization barriers and radical structural parameters (e.\u2009g., linker bond length and bond angle). A strong correlation is found between the radical attack trajectory angle and the reaction barrier heights, i.\u2009e., cyclization preference. Finally, the influence of stereoelectronic effects on the two radical cyclization pathways is further investigated in stereoisomers of hypervalent silicon system, which provides novel insight into cyclization control.<\/jats:p>","DOI":"10.1002\/cphc.202300426","type":"journal-article","created":{"date-parts":[[2023,7,1]],"date-time":"2023-07-01T08:43:55Z","timestamp":1688201035000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["6\u2010Endo\u2010dig versus 5\u2010exo\u2010dig: Exploring Radical Cyclization Preference with First\u2010, Second\u2010, and Third\u2010row Linkers using High\u2010level Quantum Chemical Methods"],"prefix":"10.1002","volume":"24","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7987-2773","authenticated-orcid":false,"given":"Abdulkader","family":"Baroudi","sequence":"first","affiliation":[{"name":"College of Engineering and Technology American University of the Middle East  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