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When activated with NIS and catalytic TMSOTf in the presence of methanol, the stereoselectivity of <jats:italic>O<\/jats:italic>\u2010glycosylation displays an intriguing dependence on the reaction temperature, with an increased preference for formation of the \u03b1\u2010glycoside at higher temperatures. Using a combination of vt\u2010NMR spectroscopy and DFT calculations, we show how a simple mechanistic model, based on competing reactions of the iodinated thioglycoside, can explain the main features of the temperature dependence. In this model, the increased selectivity at high temperature is attributed to differences among the entropy and energy terms of the competing reaction pathways. Neighbouring\u2010group participation (giving an intermediate acyloxonium ion) plays an increasingly dominant role as temperature is raised. The general features of this kinetic regime may also apply more broadly to other glycosylations that likewise favour \u03b1\u2010glycoside formation at high temperature.<\/jats:p>","DOI":"10.1002\/chem.202400331","type":"journal-article","created":{"date-parts":[[2024,7,8]],"date-time":"2024-07-08T22:27:32Z","timestamp":1720477652000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Origins of Temperature\u2010Dependent Anomeric Selectivity in Glycosylations with an L\u2013Idose Thioglycoside"],"prefix":"10.1002","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8038-634X","authenticated-orcid":false,"given":"Nicholas W.","family":"See","sequence":"first","affiliation":[{"name":"School of Chemistry and Molecular Biosciences The University of Queensland  Brisbane 4072 Queensland Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7482-0509","authenticated-orcid":false,"given":"Ras Baizureen","family":"Roseli","sequence":"additional","affiliation":[{"name":"School of Chemistry and Molecular Biosciences The University of Queensland  Brisbane 4072 Queensland Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7178-8101","authenticated-orcid":false,"given":"Norbert","family":"Wimmer","sequence":"additional","affiliation":[{"name":"School of Chemistry and Molecular Biosciences The University of Queensland  Brisbane 4072 Queensland Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tri T.","family":"Le","sequence":"additional","affiliation":[{"name":"School of Chemistry and Molecular Biosciences The University of Queensland  Brisbane 4072 Queensland Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1911-0501","authenticated-orcid":false,"given":"Elizabeth H.","family":"Krenske","sequence":"additional","affiliation":[{"name":"School of Chemistry and Molecular Biosciences The University of Queensland  Brisbane 4072 Queensland Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3306-2550","authenticated-orcid":false,"given":"Vito","family":"Ferro","sequence":"additional","affiliation":[{"name":"School of Chemistry and Molecular Biosciences The University of Queensland  Brisbane 4072 Queensland Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,9,3]]},"reference":[{"key":"e_1_2_8_1_1","unstructured":"\u00a0"},{"key":"e_1_2_8_2_2","doi-asserted-by":"crossref","unstructured":"T. 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