2026-10-13T00:00:04Z https://api.figshare.com/v2/oai

oai:figshare.com:article/33669015 2026-09-12T15:12:40Z category_1 category_4 category_39 category_46 category_135 portal_63 item_type_3 month_year_09_2026

Conformational Locking Enables Chemoselective Direct 2‑Deoxyglycosylation of C‑4 Equatorial Glycals under Bi-Catalysis Ankit Yadav (8367510) Rajat Yadav (22439765) Aakanksha Gurawa (7916321) Sudhir Kashyap (1566073) Biophysics Biochemistry Ecology Immunology Computational Biology thereby favoring 1 sup >< b oxocarbenium ion conformations otf )< sub illustrated using carbohydrates glycosyl species revealed conformationally constrained protecting conformational locking restricts b >< sup >- fused 3 c ‑ 4 equatorial </ italic equatorial </ formidable c >- xylal trans </ n </ h </ protected l natural products mechanistic insights group strategy ferrier pathway distinctive structures We demonstrate the chemoselective 2-deoxyglycosylation of formidable C-4 <i>equatorial</i> glycals enabled by a conformationally constrained protecting-group strategy. A proof-of-principle for the Bi(OTf)₃-mediated 2-deoxyglycosylation of <i>trans</i>-fused 3,4-O-TIPDS-protected l-rhamnal, d-glucal, and <i>n</i>-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 <b>⁵<i>H</i></b>_<b>4</b> glycal and ^<b>4</b><b><i>H</i></b>_<b>3</b> oxocarbenium ion conformations, thereby favoring 1,2-addition and circumventing the Ferrier pathway. 2026-09-12T00:00:00Z Dataset Dataset 10.1021/acs.orglett.6c03543.s002 https://figshare.com/articles/dataset/Conformational_Locking_Enables_Chemoselective_Direct_2_Deoxyglycosylation_of_C_4_Equatorial_Glycals_under_Bi-Catalysis/33669015 CC BY-NC 4.0