{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,10]],"date-time":"2026-09-10T05:08:59Z","timestamp":1789016939607,"version":"build-2803163510"},"reference-count":66,"publisher":"MDPI AG","issue":"17","license":[{"start":{"date-parts":[[2026,9,4]],"date-time":"2026-09-04T00:00:00Z","timestamp":1788480000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["25-23-00668"],"award-info":[{"award-number":["25-23-00668"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]},{"award":["25-23-00668"],"award-info":[{"award-number":["25-23-00668"]}],"id":[{"id":"https:\/\/ror.org\/03y2gwe85","id-type":"ROR","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The synthesis and multi-step spectroscopic characterization of diastereomeric 3-spiro-1,2,4-trioxolanes obtained by Griesbaum co-ozonolysis of sitostanone O-methyl oxime with two types of fluorinated ketones are reported. The reaction furnished four possible diastereomers that differ in the \u03b1\/\u03b2 orientation of the peroxide bridge relative to the steroid A-ring and in the syn\/anti orientation of the trifluoromethyl group at C5\u2032. A chemometric PLS2 approach, linking experimental and DFT-calculated 13C chemical shifts, was used for the objective stereochemical assignment of each diastereomer in the inseparable mixtures. Single-crystal X-ray analysis of the isolated 3R,5\u2032R and 3R,5\u2032S stereoisomeric pair (\u03b1-anti and \u03b1-syn ozonides) provided unambiguous absolute configurations that validated the stereochemical assignments obtained by the combined NMR\/DFT\/PLS2 approach. This integrated synthetic, crystallographic, spectroscopic, and chemometric methodology provides reliable configurational assignment in complex spiro-peroxide mixtures and expands the analytical toolkit for such systems.<\/jats:p>","DOI":"10.3390\/molecules31173105","type":"journal-article","created":{"date-parts":[[2026,9,4]],"date-time":"2026-09-04T16:07:32Z","timestamp":1788538052000},"page":"3105","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Synthesis and Stereochemical Assignment of Diastereomeric Steroidal Spiro-1,2,4-trioxolanes with Sitostanone Motif Using PLS2 Chemometric Analysis of DFT-Calculated and Experimental 13C NMR Data"],"prefix":"10.3390","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9223-508X","authenticated-orcid":false,"given":"Alexander","family":"Lobov","sequence":"first","affiliation":[{"name":"Ufa Institute of Chemistry of the Ufa Federal Research Centre of the Russian Academy of Sciences, 71, pr. Oktyabrya, 450054 Ufa, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2910-6805","authenticated-orcid":false,"given":"Anastasiya","family":"Kerimova","sequence":"additional","affiliation":[{"name":"Ufa Institute of Chemistry of the Ufa Federal Research Centre of the Russian Academy of Sciences, 71, pr. Oktyabrya, 450054 Ufa, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7176-505X","authenticated-orcid":false,"given":"Irina","family":"Smirnova","sequence":"additional","affiliation":[{"name":"Ufa Institute of Chemistry of the Ufa Federal Research Centre of the Russian Academy of Sciences, 71, pr. Oktyabrya, 450054 Ufa, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dmitriy","family":"Polovyanenko","sequence":"additional","affiliation":[{"name":"N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 630090 Novosibirsk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Irina","family":"Bagryanskaya","sequence":"additional","affiliation":[{"name":"N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 630090 Novosibirsk, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5606-1588","authenticated-orcid":false,"given":"Oxana","family":"Kazakova","sequence":"additional","affiliation":[{"name":"Ufa Institute of Chemistry of the Ufa Federal Research Centre of the Russian Academy of Sciences, 71, pr. Oktyabrya, 450054 Ufa, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2026,9,4]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Dembitsky, V.M. (2023). 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