Synthetic Methodologies toward Aldoheptoses and Their Applications to the Synthesis of Biochemical Probes and LPS Fragments

Tikad, Abdellatif; Vincent, Stéphane

doi:10.1002/9783527658947.ch2

Cited by 5 publications

(3 citation statements)

References 129 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Our group has been involved in the synthesis of both l ‐ and d ‐heptose scaffolds in the context of the inhibition of the enzymes of the bacterial heptose biosynthetic pathway . HBP being 6‐ d configured, we decided to follow the well‐established methodology based on the dihydroxylation of intermediate alkene 12 easily obtained, in large scale, by a Wittig methylenation of the corresponding aldehyde derived from commercial d ‐mannoside 11 in four steps (Scheme 1) .…”

Section: Resultsmentioning

confidence: 99%

Nonhydrolyzable Heptose Bis‐ and Monophosphate Analogues Modulate Pro‐inflammatory TIFA‐NF‐κB Signaling

Liang

Wei

et al. 2020

ChemBioChem

Self Cite

View full text Add to dashboard Cite

d-Glycero-d-manno-heptose-1β,7-bisphosphate (HBP) and dglycero-d-manno-heptose-1β-phosphate (H1P) are bacterial metabolites that were recently shown to stimulate inflammatory responses in host cells through the activation of the TIFAdependent NF-kB pathway. To better understand structurebased activity in relation to this process, a family of nonhydrolyzable phosphonate analogues of HBP and H1P was synthesized. The inflammation modulation by which these molecules induce the TIFA-NF-kB signal axis was evaluated in vivo at a low-nanomolar concentration (6 nM) and compared to that of the natural metabolites. Our data showed that three phosphonate analogues had similar stimulatory activity to HBP, whereas two phosphonates antagonized HBP-induced TIFA-NF-kB signaling. These results open new horizons for the design of pro-inflammatory and innate immune modulators that could be used as vaccine adjuvant.

show abstract

Section: Resultsmentioning

confidence: 99%

Nonhydrolyzable Heptose Bis‐ and Monophosphate Analogues Modulate Pro‐inflammatory TIFA‐NF‐κB Signaling

Liang

Wei

et al. 2020

ChemBioChem

Self Cite

View full text Add to dashboard Cite

show abstract

“…Adding a handle to HMP to form molecular probes at O- 7 has not yet been reported; however, heptose probes have been synthesized previously, especially for the study of LPS . One approach was to oxidize the nonreducing end of l - glycero - d - manno heptose to the acid followed by a condensation reaction leading to an amide with alkyne or azide functional groups available for potential click chemistry .…”

Section: Introductionmentioning

confidence: 99%

d-Glycero-β-d-mannoheptose Phosphate 7-O-Modifications

et al. 2021

View full text Add to dashboard Cite

Pathogen-associated molecular patterns activate the immune system via pattern recognition receptors. Recently, newly discovered pathogen-associated molecular patterns, d-glycero-β-d-mannoheptose phosphate and d-glycero-β-d-mannoheptose 1,7-biphosphate, were shown to induce a TRAF-interacting protein with a forkhead-associated domain-dependent immune response in human embryonic kidney cells and colonic epithelial cells. Concurrently, ADP-heptose was shown to bind α-kinase 1 and activate TIFA via phosphorylation leading to an immune cascade to ultimately activate NF-κB. These pathogen-associated molecular patterns have raised interest in the pharmaceutical industry for their potential use as immunomodulators. However, little is understood about the host cell uptake of d-glycero-β-d-mannoheptose phosphate, d-glycero-β-d-mannoheptose 1,7-biphosphate, and ADP-heptose in vivo and derivatives of these molecules are needed to interrogate this. In this regard, herein we describe 7-O-modifications of d-glycero-β-d-mannoheptose phosphate to produce molecular probes toward the development of a useful toolbox for biologists. A convergent strategy that involves introduction of a substituent at O-7 before alkene oxidation was investigated and proved successful in the generation of a range of molecular probes.

show abstract

“…Synthesis of l , d -Hep and d , d -Hep building blocks often relied on the homologation strategy by one-carbon elongation of the mannose derivatives . The most common approaches include Grignard addition to the C-6 aldehyde moiety of the protected mannose derivatives, and Wittig olefination of the 1,6-dialdopyranoside substrates followed by osmium-mediated dihydroxylation or proline-catalyzed α-aminoxylation. , Occasionally, the l , d -Hep and d , d -Hep building blocks could also be synthesized by the Corey–Chaykovsky reaction via the epoxide species from the 1,6-dialdopyranoside substrates . Notably, indium-mediated acyloxyallylation of unprotected l -lyxose and d -ribose followed by ozonolysis gave access to free or peracetylated l , d -Hep and d , d -Hep in a practical manner .…”

mentioning

confidence: 99%

Synthesis of l-glycero- and d-glycero-d-manno-Heptose Building Blocks for Stereoselective Assembly of the Lipopolysaccharide Core Trisaccharide of Vibrio parahemolyticus O2

et al. 2020

View full text Add to dashboard Cite

Synthesis of bacterial cell surface l-glycero-d-manno-heptose (l,d-Hep)- and d-glycero-d-manno-heptose (d,d-Hep)-containing higher carbon sugars is a challenging task. Here, we report a convenient and efficient approach for the synthesis of the l,d-Hep and d,d-Hep building blocks. Using l-lyxose and d-ribose as starting materials, this approach features diastereoselective Mukaiyama-type aldol reactions as the key steps. On the basis of the synthetic l,d-Hep and d,d-Hep building blocks, we achieved the first stereoselective synthesis of the unique α-l,d-Hep-(1→3)-α-d,d-Hep-(1→5)-α-Kdo core trisaccharide of the lipopolysaccharide of Vibrio parahemolyticus O2.

show abstract

Synthetic Methodologies toward Aldoheptoses and Their Applications to the Synthesis of Biochemical Probes and LPS Fragments

Cited by 5 publications

References 129 publications

Nonhydrolyzable Heptose Bis‐ and Monophosphate Analogues Modulate Pro‐inflammatory TIFA‐NF‐κB Signaling

Nonhydrolyzable Heptose Bis‐ and Monophosphate Analogues Modulate Pro‐inflammatory TIFA‐NF‐κB Signaling

d-Glycero-β-d-mannoheptose Phosphate 7-O-Modifications

Synthesis of l-glycero- and d-glycero-d-manno-Heptose Building Blocks for Stereoselective Assembly of the Lipopolysaccharide Core Trisaccharide of Vibrio parahemolyticus O2

Contact Info

Product

Resources

About