{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,10]],"date-time":"2026-09-10T05:09:14Z","timestamp":1789016954306,"version":"build-2803163510"},"reference-count":45,"publisher":"MDPI AG","issue":"18","license":[{"start":{"date-parts":[[2026,9,8]],"date-time":"2026-09-08T00:00:00Z","timestamp":1788825600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100012190","name":"Ministry of Science and Higher Education of the Russian Federation","doi-asserted-by":"crossref","award":["075-15-2024-531"],"award-info":[{"award-number":["075-15-2024-531"]}],"id":[{"id":"10.13039\/501100012190","id-type":"DOI","asserted-by":"crossref"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The pyranoside-into-furanoside (PIF) rearrangement is an uncommon but important process in carbohydrate chemistry. The quantum chemical investigation of the driving force of the recently discovered TfOH-catalyzed ring contraction revealed that it stemmed from the \u03c0\u2013\u03c0 interactions of the phenyl rings in benzoyl-protecting groups. In this study, we focused on the kinetic aspects, which included preliminary 2-O-benzoyl group rotation followed by the protonation of the endo-cyclic O5 atom. Using a combination of DFT and DLPNO-CCSDT methods, we found that in some cases, DFT may not produce adequate energies at the rate-limiting stage of the pyranoside ring opening, presumably due to inadequate modeling of Van der Waals interactions. Predicted rate constants for the PIF rearrangement of the \u03b2-O-methyl and \u03b2-S-ethyl galactosides were in agreement with NMR kinetic experiments, as the latter reacts significantly slower. The estimated constant for the \u03b2-O-phenyl galactoside supports its inability to undergo ring contraction and suggests temperatures of over 400 K for such transformation. The proposed mechanism was additionally confirmed by substituting the triflic acid with the much weaker trifluoroacetic one, which led to a drastic decrease of the reaction rate both in computations and in the experiment.<\/jats:p>","DOI":"10.3390\/molecules31183145","type":"journal-article","created":{"date-parts":[[2026,9,8]],"date-time":"2026-09-08T09:02:24Z","timestamp":1788858144000},"page":"3145","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["The Computational Study of the Mechanism of the Acid-Promoted Pyranoside-into-Furanoside Rearrangement"],"prefix":"10.3390","volume":"31","author":[{"given":"Alexey G.","family":"Gerbst","sequence":"first","affiliation":[{"name":"Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"conceptualization","vocabulary":"credit"},{"role":"methodology","vocabulary":"credit"},{"role":"validation","vocabulary":"credit"},{"role":"formal-analysis","vocabulary":"credit"},{"role":"software","vocabulary":"credit"},{"role":"investigation","vocabulary":"credit"},{"role":"data-curation","vocabulary":"credit"},{"role":"writing-original-draft","vocabulary":"credit"},{"role":"writing-review-editing","vocabulary":"credit"},{"role":"visualization","vocabulary":"credit"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3127-1087","authenticated-orcid":false,"given":"Dmitry A.","family":"Argunov","sequence":"additional","affiliation":[{"name":"Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"conceptualization","vocabulary":"credit"},{"role":"validation","vocabulary":"credit"},{"role":"formal-analysis","vocabulary":"credit"},{"role":"investigation","vocabulary":"credit"},{"role":"writing-original-draft","vocabulary":"credit"},{"role":"writing-review-editing","vocabulary":"credit"},{"role":"visualization","vocabulary":"credit"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9477-4610","authenticated-orcid":false,"given":"Vadim B.","family":"Krylov","sequence":"additional","affiliation":[{"name":"Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"conceptualization","vocabulary":"credit"},{"role":"formal-analysis","vocabulary":"credit"},{"role":"investigation","vocabulary":"credit"},{"role":"data-curation","vocabulary":"credit"},{"role":"writing-original-draft","vocabulary":"credit"},{"role":"writing-review-editing","vocabulary":"credit"},{"role":"visualization","vocabulary":"credit"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0727-4050","authenticated-orcid":false,"given":"Nikolay E.","family":"Nifantiev","sequence":"additional","affiliation":[{"name":"Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russia"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"conceptualization","vocabulary":"credit"},{"role":"resources","vocabulary":"credit"},{"role":"data-curation","vocabulary":"credit"},{"role":"writing-review-editing","vocabulary":"credit"},{"role":"supervision","vocabulary":"credit"},{"role":"project-administration","vocabulary":"credit"},{"role":"funding-acquisition","vocabulary":"credit"}]}],"member":"1968","published-online":{"date-parts":[[2026,9,8]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Mahara, G., Tian, C., Xu, X., and Zhu, J. (2022). Breakthrough of Glycobiology in the 21st Century. Front. Immunol., 13.","DOI":"10.3389\/fimmu.2022.1071360"},{"key":"ref_2","unstructured":"Varki, A., and Press, C.S.H.L. (2022). 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