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1. Stereoselective Approaches to β-Linked 2-Deoxy Sugars

   https://doi.org/10.3390/molecules30071578  

   Bennett, Clay S (April 2025, Molecules)

   This review presents a survey of recent developments in the synthesis of β-linked 2-deoxy sugars. Approaches ranging from catalysis to de novo synthesis are described, with a focus on methods developed in the last 10 years. Where relevant, the application of these technologies to synthesis and mechanistic information is discussed. Finally, it concludes with an examination of the scope and limitations of these technologies, as well as examinations about where the field should head next. 

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2. Conformational disorder in the crystal structure of methyl 2-acetamido-2-deoxy-β- D -glucopyranosyl-(1→4)–2-acetamido-2-deoxy-β- D -glucopyranoside (methyl β-chitobioside) methanol monosolvate

   https://doi.org/10.1107/S2053229624005199  

   Shit, Pradip; Tetrault, Timothy; Zhang, Wenhui; Yoon, Mi-Kyung; Oliver, Allen G; Serianni, Anthony S (July 2024, Acta Crystallographica Section C Structural Chemistry)

   Methyl 2-acetamido-2-deoxy-β-D-glucopyranosyl-(1→4)-2-acetamido-2-deoxy-β-D-glucopyranoside (methyl β-chitobioside), (IV), crystallizes from aqueous methanol at room temperature to give a structure (C₁₇H₃₀N₂O₂₂·CH₃OH) containing conformational disorder in the exocyclic hydroxymethyl group of one of its βGlcNAc residues. As observed in other X-ray structures of disaccharides containing β-(1→4)O-glycosidic linkages, inter-residue hydrogen bonding between O3H of the βGlcNAc bearing the OCH₃aglycone and O5 of the adjacent βGlcNAc is observed based on the 2.79 Å internuclear distance between the O atoms. The structure of (IV) was compared to that determined previously for 2-acetamido-2-deoxy-β-D-glucopyranosyl-(1→4)-2-acetamido-2-deoxy-β-D-glucopyranose (β-chitobiose), (III). TheO-glycosidic linkage torsion angles,phi(ϕ) andpsi(ψ), in (III) and (IV) differ by 6–8°. TheN-acetyl side chain conformation in (III) and (IV) shows some context dependence, with the C1—C2—N—C_cartorsion angle 10–15° smaller for the βGlcNAc residue involved in the internalO-glycosidic linkage. In (IV), conformational disorder is observed in the exocyclic hydroxymethyl (–CH₂OH) group in the βGlcNAc residue bearing the OCH₃aglycone, and a fitting of the electron density indicates an approximate 50:50 distribution of thegauche–gauche(gg) andgauche–trans(gt) conformers in the lattice. Similar behavior is not observed in (III), presumably due to the different packing structure in the vicinity of the –CH₂OH substituent that affects its ability to hydrogen bond to proximal donors/acceptors. Unlike (IV), a re-examination of the previously reported electron density of (III) revealed conformational disorder in theN-acetyl side chain attached to the reducing-end βGlcNAc residue caused by rotation about the C2—N bond. 

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3. Phenanthroline-Catalyzed Stereoselective Formation of α-1,2- cis 2-Deoxy-2-Fluoro Glycosides

   https://doi.org/10.1021/acscatal.0c04381  

   DeMent, Paul M.; Liu, Chenlu; Wakpal, Joseph; Schaugaard, Richard N.; Schlegel, H. Bernhard; Nguyen, Hien M. (February 2021, ACS Catalysis)

   null (Ed.)
4. SuFEx-Enabled Direct Deoxy-Diversification of Alcohols

   https://doi.org/10.1021/acs.orglett.4c01016  

   Odoh, Amaechi Shedrack; Keeler, Courtney; Kim, Byoungmoo (May 2024, Organic Letters)
5. D -Mannosamine hydrochloride (2-amino-2-deoxy- D -mannose hydrochloride): ionic hydrogen bonding in saccharides involving chloride and aminium ions

   https://doi.org/10.1107/S2053229622002121  

   Lin, Jieye; Oliver, Allen G.; Serianni, Anthony S. (April 2022, Acta Crystallographica Section C Structural Chemistry)

   D-Mannosamine hydrochloride (2-amino-2-deoxy-D-mannose hydrochloride), C 6 H 14 NO 5 + ·Cl − , (I), crystallized from a methanol/ethyl acetate/ n -hexane solvent mixture at room temperature in a 4 C 1 chair conformation that is slightly distorted towards the C3,O5 B form. A comparison of the structural parameters of (I) with the corresponding parameters in α-D-glucosamine hydrochloride, (II), and β-D-galactosamine hydrochloride, (III)/(III′), was undertaken to evaluate the effects of ionic hydrogen bonding on structural properties. Three types of ionic hydrogen bonds are present in the crystals of (I)–(III)/(III′), i.e. N + —H...O, N + —H...Cl − , and O—H...Cl − . The exocyclic structural parameters in (I), (II), and (III)/(III′) appear to be most influenced by this bonding, especially the exocyclic hydroxy groups, which adopt eclipsed conformations enabled by ionic hydrogen bonding to the chloride anion. Anomeric disorder was observed in crystals of (I), with an α:β ratio of 37:63. However, anomeric configuration appears to exert minimal structural effects; that is, bond lengths, bond angles, and torsion angles are essentially identical in both anomers. The observed disorder at the anomeric C atom of (I) appears to be caused by the presence of the chloride anion and atom O3 or O4 in proximal voids, which provide opportunities for hydrogen bonding to atom O1 in both axial and equatorial orientations. 

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