Lactose as an inexpensive starting material for the preparation of aldohexos-5-uloses: synthesis of l-ribo and d-lyxo derivatives

Guazzelli, Lorenzo; Catelani, Giorgio; D’Andrea, Felicia

doi:10.1016/j.carres.2009.11.027

Cited by 17 publications

(12 citation statements)

References 27 publications

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“…In particular, in a complete stereoselective fashion, inositols of six different configurations characterised by the 2,3,6- cis arrangement of three substituents were obtained from aldohexos-5-uloses. Furthermore, the formal synthesis of L- chiro -inositol could be considered as achieved starting from known D- lyxo -aldohexos-5-ulose derivatives [37,50]. Even if in some cases yields of isolated compounds are not too high, this sugar-based approach gives access directly to enantiomerically pure inositol derivatives.…”

Section: Resultsmentioning

confidence: 99%

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

D’Andrea

Catelani

Guazzelli

et al. 2016

Beilstein J. Org. Chem.

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The intramolecular aldol condensation of aldohexos-5-ulose derivatives of the D-xylo and L-ribo stereoseries has been studied. Only one of the four possible inososes was isolated from both stereoseries in reasonable yields (30–38%). The results obtained, together with the previous findings for the L-arabino and L-lyxo stereoseries, allowed for the rationalisation of a mechanism of the reaction based on open-transition-state models and electron-withdrawing inductive effects. Complementary reductions of the intermediate inososes were possible by changing the reaction conditions, and two isomeric inositol derivatives were obtained with complete stereoselection from each inosose. The presented approach permits us to control the configuration of three out of the six stereocentres of the inositol frame and gives access to seven of the nine inositols. Noteworthy, for the D-xylo derivative, the two-step sequence (condensation followed by reduction with NaBH(OAc)3) represents the biomimetic synthesis of myo-inositol. Furthermore, the sugar-based pathway leads directly to enantiomerically pure selectively protected inositols and does not require any desymmetrisation procedure which is needed when myo-inositol and other achiral precursors are employed as starting materials. As an example of application of the method, the indirect selective protection of secondary inositols’ hydroxy functions, by placing specific protecting groups on the aldohexos-5-ulose precursor has been presented.

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Section: Resultsmentioning

confidence: 99%

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

D’Andrea

Catelani

Guazzelli

et al. 2016

Beilstein J. Org. Chem.

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“…A mechanism involving attack of the unassigned carboxylate directly at the site of initial charge development on carbon 5 was ruled unlikely, both because of the poor placement of this group relative to carbon 5 in the substrate-bound crystal structure (10) as well as the KIE arising from deuterium for hydrogen substitution at C1 suggesting involvement of this center in the rate-determining step of the reaction. Attack of the C2 hydroxyl group at C5 to form a bridged intermediate was also ruled unlikely on the basis of crystallographic evidence against the adoption of an appropriate conformation in the enzyme active site, despite precedence also existing for such mechanisms in the nonenzymatic literature (50,51). Furthermore, such a mechanism would not explain the KIE from deuterium for hydrogen substitution at C1.…”

Section: Toward the Mechanism Of Unsaturated Glucuronyl Hydrolasementioning

confidence: 99%

Mechanistic Investigations of Unsaturated Glucuronyl Hydrolase from Clostridium perfringens

Jongkees

Yoo

Withers

2014

Journal of Biological Chemistry

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Background: Unsaturated glucuronyl hydrolases (UGL) from GH88 are bacterial enzymes involved in the degradation of glycosaminoglycans and are virulence factors. Results: Mechanistic data inconsistent with the currently accepted mechanism of UGL are presented. Conclusion: A revised mechanism is proposed to explain all mechanistic data published to date. Significance: Understanding of the mechanism of UGL may allow design of bacteriostatic agents.

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“…In a telescoped procedure ( Scheme 6 ) beginning from 3,4-isopropylidene protected compound 7 , the 2-OH was oxidised to the corresponding ulose with N -methylmorpholine N -oxide (NMO) and catalytic tetrapropylammonium perruthenate (TPAP) [ 24 , 25 , 26 , 27 ]. This was then used in a Grignard reaction with vinylmagnesium bromide, followed by acidic cleavage of the isopropylidene group, yielding triols 8 (14%) and 10 (50%) over 3 steps.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Fucose Derivatives with Thiol Motifs towards Suicide Inhibition of Helicobacter pylori

et al. 2020

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The syntheses of six thiol-exhibiting monosaccharides towards suicide inhibition of Helicobacter pylori are reported. Blood group Antigen Binding Adhesin (BabA), a bacterial membrane-bound lectin, binds to human ABO and Lewis b blood group structures displayed on the surface of host epithelial cells. Crystal structures of the carbohydrate-recognition domain revealed a conserved disulfide bonded loop that anchors a critical fucose residue in these blood group structures. Disruption of this loop by N-acetylcysteine results in reduced BabA-mediated adherence to human gastric tissue sections and attenuated virulence in Lewis b-expressing transgenic mice. With a view of creating specific inhibitors of the lectin, we designed and successfully synthesised six fucose-derived compounds with thiol motifs to engage in a thiol-disulfide exchange with this disulfide bond of BabA and form a glycan-lectin disulfide linkage. Branching and extending the fucose backbone with 2- and 3-carbon thiol motifs delivered a range of candidates to be tested for biological activity against BabA.

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Lactose as an inexpensive starting material for the preparation of aldohexos-5-uloses: synthesis of l-ribo and d-lyxo derivatives

Cited by 17 publications

References 27 publications

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

Mechanistic Investigations of Unsaturated Glucuronyl Hydrolase from Clostridium perfringens

Synthesis of Fucose Derivatives with Thiol Motifs towards Suicide Inhibition of Helicobacter pylori

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