The Glycofuranosides

Green, John W.

doi:10.1016/s0096-5332(08)60316-1

Cited by 35 publications

(8 citation statements)

References 170 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Importantly, forming such HB chain amplifies its stability via hydrogen-bond cooperativity effects. 69 Within this hydrogen-bonded network, the O1•••H2O2 interaction is indicated to be the strongest, based on the largest values of ΔE ij (2) energy and σ* O2−H2 occupancy (SI Table S5). The NBO quantities are coupled with this H-bond geometric parameters: r(O1 S5, can serve a measure of HB ideality: 180°corresponds to a perfect hydrogen bond 70 ).…”

Section: Resultsmentioning

confidence: 98%

“…A distinct structural feature of the former species is a more pronounced tendency toward linearity exhibited by one or two H-bonds, with the OH•••O angle of 139−145°(showed by the HBs of water 71 ) and H•••O distance of 1.91−1.98 Å. Such "quasi-linear" H-bonds are coupled with the increased value of ΔE ij (2) energy (relative to those for the β-pyranoses), as arising from the n O1 → σ* O3−H3 or n O2 → σ* O4−H4 or n O4 → σ* O2−H2 interaction.…”

Section: Resultsmentioning

confidence: 99%

“…Although the anomeric effect is usually invoked to a stabilization of six-membered rings, 67 SI Table S6 reveals that the relevant hyperconjugative interactions are also significant (in terms of ΔE ij (2) values) in the four low-energy (fivemembered ring) fructofuranose structures having the "quasiaxial" orientation of −OH at C2 (Figure 3). For these furanoses, the exo and endo effects can be related to the n O2 → σ* C2−O5 and n O5 → σ* C2−O2 hyperconjugations, respectively (see Figure 10).…”

Section: Resultsmentioning

confidence: 99%

“…A biologically relevant fructose structure corresponds to a furanose (or furanoside). 2 D-Fructose is one of the most common monosaccharides, found in fruits and vegetables, being a constituent of disaccharide sucrose and the building block of polysaccharides such as inulin and levan. 3 It is the sweetest natural sugar known, widely used in the food industry as high-fructose corn syrup (HFCS).…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Cyclic and Acyclic Fructose Conformers in the Gas Phase: A Large-Scale Second-Order Perturbation Theory Study

Szczepaniak

Moc

2014

J. Phys. Chem. A

View full text Add to dashboard Cite

We performed large-scale second-order perturbation theory gas-phase calculations to study about five hundred structures of D-fructose. The two lowest energy fructose structures identified are β-pyranoses possessing (2)C5 chair, with ΔG(298 K) of 6 kJ/mol, differing in orientation of the equatorially positioned hydroxymethyl group, gt and g'g, where the gt rotamer is the global minimum, consistent with the recent microwave spectroscopy study. We have found that interconversions from the fructose global minimum to the second and third most stable β-pyranose rotamers involve the energy barriers of ca. 30 kJ/mol. Among numerous fructofuranose conformers discovered (about 250), a pair of the ((3)T2) α- and (E3) β-anomers are energetically most preferred and lie at least 12 kJ/mol above the global minimum. We also found that the fructose open-chain structures lie significantly higher in energy than the most stable cyclic species. The commonly used M06-2X density functional performs well compared to MP2 and G4 theory at identifying the low-energy fructose minima, including the global one, and at reproducing their intramolecular H-bond geometric parameters. The lowest-energy gas-phase pyranose and furanose structures of fructose benefit from stabilization due to the cooperative or quasi-linear H-bonding and both endo and exo anomeric effects.

show abstract

Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Cyclic and Acyclic Fructose Conformers in the Gas Phase: A Large-Scale Second-Order Perturbation Theory Study

Szczepaniak

Moc

2014

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…Another method used acyclic glycosyl dithioacetals as precursors in the synthesis of glycosyl furanosides (Fischer, 1894;Green, 1966;Pacsu and Green, 1936). One example involved the preparation of 1-chloro-1-(ethylthio) derivatives (10) of D-glucose and Dgalactose from the corresponding dithioacetal pentaacetates ( Figure 3, Wolfrom et al, 1944).…”

Section: Introductionmentioning

confidence: 99%

Simple and Efficient Method for the Synthesis of Galactofuranosides

Completo

Sangalang

Pique

et al. 2017

KIMIKA

View full text Add to dashboard Cite

An efficient and improved one-pot method for the synthesis of galactofuranosides via iodine-promoted cyclization of galactose diethyl dithioacetal in the presence of alcohol, acting both as solvent and nucleophile, is described. The reaction is carried out at room temperature. Alcohols, such as methanol, cyclohexanol and tert-butanol, were used as nucleophiles for the reaction using 2%, 3% and 5% iodine promoter, respectively. A key finding in this study was that the iodine-promoted cyclization of galactose diethyl dithioacetal with alcohol led to selective formation of β-galactofuranoside allowing the efficient preparation of derivatives of this monosaccharide.

show abstract

A General and Diastereoselective Synthesis of 1,2-cis-Hexofuranosides from 1,2-trans-Thiofuranosyl Donors

Gelin

Ferrières

Plusquellec³

2000

Eur. J. Org. Chem.

View full text Add to dashboard Cite

The general formation of 1,2‐trans‐thioglycofuranosides derived from D‐galactose, D‐glucose and D‐mannose was readily accomplished starting from the corresponding alkyl glycofuranosides via per‐O‐acetyl‐hexofuranoses as key synthons. Glycosidation of ethyl or phenyl perbenzylated 1,2‐trans‐thiofuranosides afforded disaccharides containing a nonreducing 1,2‐cis‐hexofuranosyl unit, i.e. α‐D‐galactosyl, α‐D‐glucosyl or β‐D‐mannosyl, with interesting diastereoselectivities. Activation of the thiofuranosyl donors was performed by N‐iodosuccinimide and a catalytic amount of tin(II) trifluoromethanesulfonate.

show abstract

The Glycofuranosides

Cited by 35 publications

References 170 publications

Cyclic and Acyclic Fructose Conformers in the Gas Phase: A Large-Scale Second-Order Perturbation Theory Study

Cyclic and Acyclic Fructose Conformers in the Gas Phase: A Large-Scale Second-Order Perturbation Theory Study

Simple and Efficient Method for the Synthesis of Galactofuranosides

A General and Diastereoselective Synthesis of 1,2-cis-Hexofuranosides from 1,2-trans-Thiofuranosyl Donors

Contact Info

Product

Resources

About