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. 2025 Sep 12;10(37):42999-43011.
doi: 10.1021/acsomega.5c05437. eCollection 2025 Sep 23.

Structural Bias Effect On Azidation at C‑1 and C‑2 of Alkyl-3,6-anhydro‑d‑hexofuranosides: Synthetic Approach to Natural Products and Derivatives

Ratul Hore  1 , Koushik Bit  1 , Rajatava Pan  1 , Tapas Halder  1 , Susanta Das  1   2 , Subhadip Sett  1 , Tapas Bera  3 , Abhinash Subba  1 , Joykrishna Maity  1
Affiliations

Structural Bias Effect On Azidation at C‑1 and C‑2 of Alkyl-3,6-anhydro‑d‑hexofuranosides: Synthetic Approach to Natural Products and Derivatives

Ratul Hore et al. ACS Omega. .

Abstract

3,6-Anhydro hexofuranose sugars are the structural motif of natural product furanodictines A-B and sauropunols A-D, F, and H. Conversion of the 2-hydroxyl group of alkyl-3,6-anhydro-5-O-benzoyl-d-glucofuranosides to triflate intermediates followed by azidation reaction yielded 2-deoxy-2-azido derivatives when the substituents at C-1and C-2 are in cis relation; on the other hand, in the case of trans substituents, the products were α-glycosyl azide analogues. A similar reaction of butyl-3,6-anhydro-5-O-benzoyl- d-mannofuranosides, obtained from the corresponding α- or β-d-glucofuranoside through appropriate oxidation and reduction reactions, yielded only 2-deoxy-2-azido products. We report here in a synthetic approach to 2-substituted sauropunols, furanodictines A-B, and related analogues, along with 1,4-disubstituted 1,2,3-triazolyl glycoconjugates and N-glycosyl amide starting from d-glucose derived precursors.

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Figures

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1
Natural 3,6-anhydro-d-hexofuranose analogues (1–10).
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2
3,6-Anhydro-d-hexofuranose core containing bioactive compounds (11–16).
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1. Previous Reports of Azidation at C-2 of Anomeric Mixture of 18
2
2. Synthesis of 2-β-Azido Sauropunol A (25) and Its Analogue (24), 2-β-Acetamido Sauropunol A (27) and Its Analogue (26), and 2-β-Azido Sauropunol C/D (28)­
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3. Synthesis of Furanodictine B (10) and Its Glycosides (29–30) and Benzoate (31) Analogue
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4. Synthesis of Glycosyl Azides (41–43) Based on 3,6-Anhydro-d-hexofuranose
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5. Synthesis of 1,4-Disubstituted Triazolyl Glycoconjugates Based on 3,6-Anhydro-d-mannofuranose (46–49)­
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6. Synthesis of N-Glycosyl Acetamides on 3,6-Anhydro-d-mannofuranose Core (50 and 52)­
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7. Synthesis of 2-β-Hydroxy- (55), 2-α-Azido- (58), 2-α-Acetamido­(59)-Sauropunol B, and Furanodictine A (9) and Its β-Anomeric Butylglycoside (60) Analogue
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8. Synthesis of 2-α-Azido Sauropunol A (66)­
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