Acceptor-influenced and donor-tuned base-promoted glycosylation

Boettcher, Stephan; Matwiejuk, Martin; Thiem, Joachim

doi:10.3762/bjoc.8.46

Cited by 6 publications

(4 citation statements)

References 12 publications

(21 reference statements)

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“…The direct glycosylation on unprotected or partially protected acceptors is suitable for assembling the linear or branched oligosaccharides straightforwardly, with minimal protection/deprotection steps by exploiting the higher reactivity of C‐6 primary OH groups . In this regard, Thiem reported a shorter route (Scheme ) synthesis of disaccharides through the base‐promoted glycosylation strategy , . Accordingly, the partially protected acceptor 8 upon deprotonation by NaH or LiH in DMF to form the intermediate oxyanion, which upon reaction with glycosylation donor 9 forms the corresponding disaccharides 10 and 11 in 37.5 % and 12.5 % yields respectively.…”

Section: Discussionmentioning

confidence: 99%

“…[71] In this regard, Thiem reported a shorter route (Scheme 3) synthesis of disaccharides through the base-promoted glycosylation strategy. [72,73] Accordingly, the partially protected acceptor 8 upon deprotonation by NaH or LiH in DMF to form the intermediate oxyanion, which upon reaction with glycosylation donor 9 forms the corresponding disaccharides 10 and 11 in 37.5 % and 12.5 % yields respectively. The uniform -stereoselectivity is attributed to an SN2like reaction by inversion of configuration at the anomeric center of the donor.…”

Section: Direct Glycosylation On Unprotected or Partially Protected Amentioning

confidence: 99%

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Glycosylation on Unprotected or Partially Protected Acceptors

Ding

Prasad²,

Wang

2020

Eur J Org Chem

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Over the last 30 years, there have been several methods developed for the synthesis of oligosaccharides, such as combinatorial synthesis, programmable one‐pot glycosylations, pre‐activation‐based chemo‐selective glycosylation strategy, random glycosylation, chemo‐enzymatic processes, and automated platforms. Distinguishing hydroxyl groups in carbohydrate monomers form the crux of oligosaccharides synthesis. The protection of hydroxyl groups stops glycosylation at undesired positions on carbohydrates, but additional steps are required to install and remove the protecting groups. The targeted functionalization of carbohydrates relies mostly on the protection of hydroxyl groups that are not supposed to undergo glycosylation and to leave the hydroxyl group unprotected where the glycosylation should occur. Numerous procedures to avoid or decrease protecting group manipulations have been developed for the synthesis of a single or an oligosaccharide library, such as glycosylation on unprotected or partially protected acceptors, and random glycosylation on unprotected acceptors. In this review, overall approaches for glycosylation on unprotected or partially protected acceptors in the synthesis of oligosaccharides and oligosaccharide libraries are summarized, the glycosylation on unprotected or partially protected carbohydrate acceptors with or without tin or boron mediation, and random glycosylation on unprotected or partially protected acceptors in solution phase or on solid phase are discussed.

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Section: Discussionmentioning

confidence: 99%

Section: Direct Glycosylation On Unprotected or Partially Protected Amentioning

confidence: 99%

Glycosylation on Unprotected or Partially Protected Acceptors

Ding

Prasad²,

Wang

2020

Eur J Org Chem

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“…69 Methyl 3-O-Benzyl-α-D-glucopyranoside (24). As described by Boettcher et al, 70 24 was synthesized using methyl 4,6-Obenzylidene-3-O-benzyl-α-D-glucopyranoside (23) (120 mg, 0.322 mmol). The product was purified with flash chromatography (petroleum ether/EtOAc, 0−100%) to yield the pure product as a white solid (75.7 mg, 0.266 mmol, 83% yield).…”

Section: 6-di-o-benzyl-d-glucopyranosementioning

confidence: 99%

Both d- and l-Glucose Polyphosphates Mimic d-myo-Inositol 1,4,5-Trisphosphate: New Synthetic Agonists and Partial Agonists at the Ins(1,4,5)P₃ Receptor

et al. 2020

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Chiral sugar derivatives are potential cyclitol surrogates of the Ca 2+ -mobilizing intracellular messenger D-myoinositol 1,4,5-trisphosphate [Ins(1,4,5)P 3 ]. Six novel polyphosphorylated analogues derived from both D-and L-glucose were synthesized. Binding to Ins(1,4,5)P 3 receptors [Ins(1,4,5)P 3 R] and the ability to release Ca 2+ from intracellular stores via type 1 Ins(1,4,5)P 3 Rs were investigated. β-D-Glucopyranosyl 1,3,4-trisphosphate, with similar phosphate regiochemistry and stereochemistry to Ins(1,4,5)P 3 , and α-D-glucopyranosyl 1,3,4-trisphosphate are full agonists, being equipotent and 23-fold less potent than Ins(1,4,5)P 3 , respectively, in Ca 2+ -release assays and similar to Ins(1,4,5)P 3 and 15-fold weaker in binding assays. They can be viewed as truncated analogues of adenophostin A and refine understanding of structure-activity relationships for this Ins(1,4,5)P 3 R agonist. L-Glucose-derived ligands, methyl α-Lglucopyranoside 2,3,6-trisphosphate and methyl α-L-glucopyranoside 2,4,6-trisphosphate, are also active, while their corresponding D-enantiomers, methyl α-D-glucopyranoside 2,3,6-trisphosphate and methyl α-D-glucopyranoside 2,4,6-trisphosphate, are inactive. Interestingly, both L-glucose-derived ligands are partial agonists: they are among the least efficacious agonists of Ins(1,4,5)P 3 R yet identified, providing new leads for antagonist development.

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“…Use of anomeric sulfonium ions as glycosyl donors (Fang et al, 2012) Oligosaccharides MALDI Fluorine-directed -galactosylation (Durantie et al, 2012) Oligosaccharides TOF (DHB) Acceptor-influenced and donor-tuned basepromoted glycosylation (Boettcher et al, 2012) Oligosaccharides TOF (DHB)…”

Section: R-tof (Thap)mentioning

confidence: 99%

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2011–2012

Harvey

2015

Mass Spectrometry Reviews

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This review is the seventh update of the original article published in 1999 on the application of MALDI mass spectrometry to the analysis of carbohydrates and glycoconjugates and brings coverage of the literature to the end of 2012. General aspects such as theory of the MALDI process, matrices, derivatization, MALDI imaging, and fragmentation are covered in the first part of the review and applications to various structural types constitute the remainder. The main groups of compound are oligo- and poly-saccharides, glycoproteins, glycolipids, glycosides, and biopharmaceuticals. Much of this material is presented in tabular form. Also discussed are medical and industrial applications of the technique, studies of enzyme reactions, and applications to chemical synthesis. © 2015 Wiley Periodicals, Inc. Mass Spec Rev 36:255-422, 2017.

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Acceptor-influenced and donor-tuned base-promoted glycosylation

Cited by 6 publications

References 12 publications

Glycosylation on Unprotected or Partially Protected Acceptors

Glycosylation on Unprotected or Partially Protected Acceptors

Both d- and l-Glucose Polyphosphates Mimic d-myo-Inositol 1,4,5-Trisphosphate: New Synthetic Agonists and Partial Agonists at the Ins(1,4,5)P₃ Receptor

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2011–2012

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Acceptor-influenced and donor-tuned base-promoted glycosylation

Cited by 6 publications

References 12 publications

Glycosylation on Unprotected or Partially Protected Acceptors

Glycosylation on Unprotected or Partially Protected Acceptors

Both d- and l-Glucose Polyphosphates Mimic d-myo-Inositol 1,4,5-Trisphosphate: New Synthetic Agonists and Partial Agonists at the Ins(1,4,5)P3 Receptor

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2011–2012

Contact Info

Product

Resources

About

Both d- and l-Glucose Polyphosphates Mimic d-myo-Inositol 1,4,5-Trisphosphate: New Synthetic Agonists and Partial Agonists at the Ins(1,4,5)P₃ Receptor