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A radical reaction network was constructed to assess nonenzymatic pathways leading to hydroxymethyl, formyl, and carboxyl oxidation products. The results show that the reactivity of methylated cytosine derivatives is governed not by isolated C\uf8ffH bond strengths alone, but by the coupled thermodynamics of radical formation, oxygen addition, hydroperoxide formation, and hydroperoxide decomposition. Hydrogen abstraction from the 5\u2010methyl substituent is the most accessible radical\u2010forming step in 1,5dmC, whereas protonation increases BDE(C\uf8ffH) values and suppresses radical formation. Hydroperoxide intermediates play an important role within the considered propagation network, with O\uf8ffO cleavage being more accessible than O\uf8ffH cleavage. The calculated reaction free energies rationalize the possible accumulation of the formyl derivative 1m5fC: this formyl derivative is formed through strongly exergonic pathways, whereas its further conversion to the carboxyl derivative 1m5caC is more thermodynamically constrained. Representative transition\u2010state calculations provide a kinetic consistency check, showing only moderate substrate\u2010dependent variations in H\u2010abstraction barriers within each model\u2010radical class. Overall, the results identify thermodynamically relevant radical intermediates, limiting steps, and product\u2010forming routes within the considered reaction network for the nonenzymatic autoxidation of methylated cytosine derivatives.\n                  <\/jats:p>","DOI":"10.1002\/jcc.70478","type":"journal-article","created":{"date-parts":[[2026,10,1]],"date-time":"2026-10-01T08:02:46Z","timestamp":1790841766000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Thermodynamic Mapping of C5\u2010Substituent Autoxidation Pathways in 1,5\u2010Dimethylcytosine: A Quantum Chemical Study"],"prefix":"10.1002","volume":"47","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2045-2536","authenticated-orcid":false,"given":"Vasilii","family":"Korotenko","sequence":"first","affiliation":[{"name":"Thermal Separation Processes TUHH  Hamburg Germany"},{"name":"Department of Chemistry LMU M\u00fcnchen  M\u00fcnchen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0534-3585","authenticated-orcid":false,"given":"Hendrik","family":"Zipse","sequence":"additional","affiliation":[{"name":"Department of Chemistry LMU M\u00fcnchen  M\u00fcnchen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,10,1]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr60143a003"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.8b00250"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.8b00395"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja403229y"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature15713"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1101\/cshperspect.a012583"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1093\/hmg\/9.16.2395"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41392-023-01537-x"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/cbic.202100651"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.5483\/BMBRep.2014.47.11.223"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr400432d"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1093\/nsr\/nwv029"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature12750"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1038\/nrg.2017.33"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1007\/s12038-019-9973-4"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1093\/nar\/gku334"},{"key":"e_1_2_8_18_1","article-title":"Introduction of Cytosine\u20105 DNA Methylation Sensitizes Cells to Oxidative Damage","author":"Krwawicz J.","year":"2024","journal-title":"bioRxiv: The Preprint Server for Biology"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.3109\/10715762.2012.659248"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201902340"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/cbic.202500480"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0141-3910(98)00002-0"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.3390\/polym13132143"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo4001433"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201502384"},{"issue":"1005","key":"e_1_2_8_26_1","first-page":"218","article-title":"Kinetic Studies in the Chemistry of Rubber and Related Materials. 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