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A combination of synthetic, electroanalytical, and computational experiments have been performed to gain a deeper understanding of the reaction mechanism and the structural requirements for fragmentation to occur. It was found that 2\u2010arylalcohols undergo anodic oxidation to form the corresponding aromatic radical cations, which fragment to form oxocarbenium ions and benzylic radical intermediates via mesolytic cleavage, with further anodic oxidation and trapping of the benzylic carbocation with methanol to generate the observed methyl ether products. It was also found that the electrochemical fragmentation of 2\u2010arylalkanols is promoted by structural features that stabilize the oxocarbenium ions and\/or benzylic radical intermediates formed upon mesolytic cleavage of the aromatic radical cations. With an enhanced understanding of the reaction mechanism and the structural features that promote fragmentation, it is anticipated that alternative electrosynthetic transformations will be developed that utilize this powerful, yet underdeveloped, mode of substrate activation.<\/jats:p>","DOI":"10.1002\/chem.202403413","type":"journal-article","created":{"date-parts":[[2024,9,17]],"date-time":"2024-09-17T15:55:06Z","timestamp":1726588506000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Electrochemical Deconstructive Methoxylation of Arylalcohols\u2013A Synthetic and Mechanistic Investigation"],"prefix":"10.1002","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0009-0007-4438-0593","authenticated-orcid":false,"given":"Hussain A.","family":"Maashi","sequence":"first","affiliation":[{"name":"Cardiff Catalysis Institute School of Chemistry Cardiff University  Main Building, Park Place Cardiff CF10 3AT United Kingdom"},{"name":"Department of Chemistry College of Science University of Bisha  Bisha 61922 Saudi Arabia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0918-8754","authenticated-orcid":false,"given":"Toby","family":"Lewis\u2010Atwell","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Bath  Claverton Down, Bath BA2 7AY United Kingdom E-mails"},{"name":"Department of Computer Science University of Bath  Claverton Down, Bath BA2 7AY United Kingdom"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"James","family":"Harnedy","sequence":"additional","affiliation":[{"name":"Cardiff Catalysis Institute School of Chemistry Cardiff University  Main Building, Park Place Cardiff CF10 3AT United Kingdom"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2116-7929","authenticated-orcid":false,"given":"Matthew N.","family":"Grayson","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Bath  Claverton Down, Bath BA2 7AY United Kingdom E-mails"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6453-7531","authenticated-orcid":false,"given":"Louis C.","family":"Morrill","sequence":"additional","affiliation":[{"name":"Cardiff Catalysis Institute School of Chemistry Cardiff University  Main Building, Park Place Cardiff CF10 3AT United Kingdom"},{"name":"Department of Chemistry University of Bath  Claverton Down, Bath BA2 7AY United Kingdom E-mails"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,10,30]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"For selected reviews see:"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscentsci.0c01532"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1CS00223F"},{"key":"e_1_2_7_4_1","unstructured":"For selected reviews see:"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.9b00539"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41570-022-00372-y"},{"key":"e_1_2_7_7_1","unstructured":"For selected reviews see:"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b08856"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41570-017-0077"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/C8CS00379C"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00515a064"},{"key":"e_1_2_7_12_1","unstructured":"For selected reviews see:"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar980014y"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/poc.1096"},{"key":"e_1_2_7_15_1","unstructured":"For pioneering early work see:"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF00960694"},{"key":"e_1_2_7_17_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF00957996"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF00699992"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF00697143"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF02495257"},{"key":"e_1_2_7_21_2","unstructured":"Y.\u2005N. 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