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A proof-of-principle for the Bi(OTf)3-mediated 2-deoxyglycosylation of trans-fused 3,4-O-TIPDS-protected l-rhamnal, d-glucal, and d-xylal is illustrated using carbohydrates, amino-acids, and bioactive-natural products, providing structurally diverse 2-deoxy and 2,6-dideoxyglycoconjugates. Mechanistic insights into the distinctive structures of the glycosyl species revealed that conformational locking restricts the accessible 5H4 glycal and 4H3 oxocarbenium ion conformations, thereby favoring 1,2-addition and circumventing the Ferrier pathway.<\/jats:p>","DOI":"10.1021\/acs.orglett.6c03543","type":"journal-article","created":{"date-parts":[[2026,9,12]],"date-time":"2026-09-12T16:02:34Z","timestamp":1789228954000},"page":"12016-12021","source":"Crossref","is-referenced-by-count":0,"title":["Conformational\nLocking Enables Chemoselective Direct\n2-Deoxyglycosylation of C-4\n                    <i>Equatorial<\/i>\n                    Glycals under Bi-Catalysis"],"prefix":"10.1021","volume":"28","author":[{"given":"Ankit","family":"Yadav","sequence":"first","affiliation":[{"name":"Carbohydrate Chemistry Research Laboratory (CCRL) , , ,","place":["Jaipur, India, 302017"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rajat","family":"Yadav","sequence":"additional","affiliation":[{"name":"Carbohydrate Chemistry Research Laboratory (CCRL) , , ,","place":["Jaipur, India, 302017"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Aakanksha","family":"Gurawa","sequence":"additional","affiliation":[{"name":"Carbohydrate Chemistry Research Laboratory (CCRL) , , ,","place":["Jaipur, India, 302017"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7722-8554","authenticated-orcid":true,"given":"Sudhir","family":"Kashyap","sequence":"additional","affiliation":[{"name":"Carbohydrate Chemistry Research Laboratory (CCRL) , , ,","place":["Jaipur, India, 302017"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,12]]},"reference":[{"key":"2026092510103273000_cit1a","doi-asserted-by":"crossref","first-page":"367","DOI":"10.1002\/9783527618255.ch15","volume-title":"Carbohydrates\nin Chemistry and Biology","author":"Veyrie\u0300res","year":"2000"},{"key":"2026092510103273000_cit1b","first-page":"2393","volume-title":"Glycoscience:\nChemistry and Chemical Biology","author":"Lindhorst","year":"2001"},{"key":"2026092510103273000_cit1c","doi-asserted-by":"publisher","first-page":"590","DOI":"10.1016\/S1367-5931(02)00367-8","article-title":"Mechanisms of Enzymatic C-O Bond Cleavages in Deoxyhexose\nBiosynthesis","volume":"6","author":"He","year":"2002","journal-title":"Curr. 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