One-Pot Relay Glycosylation

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(12), P. 5498 - 5503

Published: March 9, 2020

A novel one-pot relay glycosylation has been established. The protocol is characterized by the construction of two glycosidic bonds with only one equivalent triflic anhydride. This method capitalizes on in situ generated cyclic-thiosulfonium ion as activator, which directly activates newly formed thioglycoside pot. wide range substrates are well-accommodated to furnish both linear and branched oligosaccharides. synthetic utility advantage this have demonstrated rapid access naturally occurring phenylethanoid glycoside kankanoside F resin merremoside D.

Language: Английский

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Merging Reagent Modulation and Remote Anchimeric Assistance for Glycosylation: Highly Stereoselective Synthesis of α‐Glycans up to a 30‐mer

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(22), P. 12597 - 12606

Published: March 25, 2021

The efficient synthesis of long, branched, and complex carbohydrates containing multiple 1,2-cis glycosidic linkages is a long-standing challenge. Here, we report merging reagent modulation 6-O-levulinoyl remote anchimeric assistance glycosylation strategy, which successfully applied to the first highly stereoselective branched Dendrobium Huoshanense glycans linear Longan up 30 contiguous glucosidic bonds. DFT calculations shed light on origin much higher stereoselectivities glucosylation with group than 6-O-acetyl or 6-O-benzoyl groups. Orthogonal one-pot strategy based glycosyl ortho-alkynylbenzoates ortho-(1-phenylvinyl)benzoates has been demonstrated in glycans, precluding such issues as aglycon transfer inherent orthogonal thioglycosides.

Language: Английский

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Automated Quantification of Hydroxyl Reactivities: Prediction of Glycosylation Reactions

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(22), P. 12413 - 12423

Published: Feb. 26, 2021

Abstract The stereoselectivity and yield in glycosylation reactions are paramount but unpredictable. We have developed a database of acceptor nucleophilic constants (Aka) to quantify the nucleophilicity hydroxyl groups influenced by steric, electronic structural effects, providing connection between experiments computer algorithms. subtle reactivity differences among on various carbohydrate molecules can be defined Aka, which is easily accessible simple convenient automation system assure high reproducibility accuracy. A diverse range donors acceptors with well‐defined promoters were organized processed designed software program “GlycoComputer” for prediction without involving sophisticated computational processing. importance Aka was further verified random forest algorithm, applicability tested synthesis Lewis skeleton show that accurately estimated.

Language: Английский

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Recent advances in transition-metal-catalyzed glycosyl cross-coupling reactions

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(12), P. 3430 - 3470

Published: Nov. 8, 2022

Language: Английский

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Plant glycosyltransferases for expanding bioactive glycoside diversity

Natural Product Reports, Journal Year: 2023, Volume and Issue: 40(7), P. 1170 - 1180

Published: Jan. 1, 2023

This article highlights previous and prospective uses for plant glycosyltransferases in generating diversifying bioactive glycosides, with implications drug discovery applications.

Language: Английский

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Chemical synthesis of oligosaccharides and their application in new drug research

European Journal of Medicinal Chemistry, Journal Year: 2023, Volume and Issue: 249, P. 115164 - 115164

Published: Feb. 1, 2023

Language: Английский

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Synergistic catalysis: An emerging concept for selective carbohydrate synthesis

Chem Catalysis, Journal Year: 2024, Volume and Issue: 4(3), P. 100891 - 100891

Published: Jan. 18, 2024

Harnessing modern catalytic concepts to address long-standing challenges in carbohydrate chemistry has garnered substantial interest from the synthetic community recent years. In particular, usage of multiple catalysts for sequential one-pot relay reactions already contributed major benefits accessing oligosaccharides past two decades. contrast, exploitation synergistic catalysis glycosciences is only its infancy. While methods combine stepwise into a single flask operation, they do not intrinsically alter reaction mechanisms. Conversely, involves creation unique mechanistic pathways by merging cycles. At nexus cycles, fertile opportunities arise bond-forming strategies that are possible within individual manifold. The realization underexploited potential expected accelerate developments field, thereby offering stereoselective entry points glycosidic chemical space was previously inaccessible.

Language: Английский

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One-Pot Assembly of Mannose-Capped Lipoarabinomannan Motifs up to 101-Mer from the Mycobacterium tuberculosis Cell Wall

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 4112 - 4122

Published: Jan. 16, 2024

Lipoarabinomannan (LAM) from the Mycobacterium tuberculosis cell envelope represents important targets for development of new therapeutic agents against tuberculosis, which is a deadly disease that has plagued mankind long time. However, accessibility long, branched, and complex lipoarabinomannan over 100-mer remains long-standing challenge. Herein, we report modular synthesis mannose-capped 101-mer M. wall using one-pot assembly strategy on basis glycosyl ortho-(1-phenylvinyl)benzoates (PVB), not only accelerates but also precludes potential problems associated with glycosylation thioglycosides. Shorter sequences including 18-mer, 19-mer, 27-mer are synthesized in-depth structure–activity relationship biological studies. Current synthetic routes highlight following features: (1) streamlined various linear branched glycans orthogonal combination N-phenyltrifluoroacetimidates, ortho-alkynylbenzoates, PVB; (2) highly stereoselective construction 10 1,2-cis-arabinofuranosyl linkages 5-O-(2-quinolinecarbonyl)-directing 1,2-cis-arabinofuranosylation via hydrogen-bond-mediated aglycone delivery strategy; (3) convergent [(18 + 19) × 2 27] LAM polysaccharide. The present work demonstrates this can streamline chemical polysaccharides.

Language: Английский

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Efficient O- and S-glycosylation with ortho-2,2-dimethoxycarbonylcyclopropylbenzyl thioglycoside donors by catalytic strain-release

Chemical Science, Journal Year: 2024, Volume and Issue: 15(10), P. 3711 - 3720

Published: Jan. 1, 2024

An efficient glycosylation reaction utilizing a meticulously designed thioglycoside has been developed. The well-established protocol was demonstrated in the total synthesis of TD139 and one-pot assembly E. coli O33 antigen tetrasaccharide.

Language: Английский

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Recent Development on Stereoselective Intramolecular O-Glycosylation Methodology±

Carbohydrate Research, Journal Year: 2025, Volume and Issue: 552, P. 109415 - 109415

Published: Feb. 10, 2025

Language: Английский

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