A combined intramolecular–intermolecular one-pot glycosylation approach for the synthesis of a branched trisaccharide

Valverde, Serafı́n; Garcia, M.‐Elisa Juarez; Gómez, Ana M.; López, J. Cristóbal

doi:10.1039/b000771o

Cited by 20 publications

(5 citation statements)

References 34 publications

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“…[a] D +32.2 (c 0.5,CHCl 3 (d,1 H,J = 7.8 Hz,Ar),7 H,Ar),9 H,Ar),2 H,Ar),2 H,H 1¢ ,H 2¢ ),5.35 (t,1 H,J =9.9 Hz,H 4¢ ),5.26 (m,1 H,H 3 ),5.22 (dd,1 H,J = 9.9,3.1 Hz,H 3¢ ),4.65 (d,1 H,J = 1.5 Hz,H 1 ),4.54 (ddd,1 H,J = 9.9,7.8,3.5 Hz,H 5¢ ),4.35 (dd,1 H,J = 7.8,3.5 Hz,H 6¢a and H 6¢b ),4.20 (m,1 H,H 2 ),4.0 (dt,1 H,J = 9.7,2.8 Hz,H 4 (s,9 H,. 13 C NMR (50 MHz, CDCl 3 ): d = 170.0 (CO),...…”

Section: Phenyl 234-tri-o-acetyl-6-o-[methyl-o-(6-o-tertbutyldimethmentioning

confidence: 99%

Study of the Regioselectivity of Intra- and Intermolecular Glycosylations of Mannoside Diol Acceptors

Cid¹,

Valverde²,

López³

et al. 2005

Synlett

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The intramolecular glycosylation of thiomannoside donors linked through C6¢ by a phthaloyl group to C3 of a diol mannoside acceptor is described. The unexpected results led us to undertake a systematic analysis of the factors affecting the regioselectivity of the intermolecular process. The substituents on the diol mannoside acceptor have been found to play an important role.The interest in carbohydrate derivatives is increasing because of their function in many biological processes. 3 The preparation of complex oligosaccharides still requires enormous effort by synthetic organic chemists, and strategies that avoid protecting group manipulations through regioselective processes would be a tremendous advance. 3c As a part of our program directed at developing regio-and stereoselective glycosylation methods based on intramolecular glycosylation 4 we applied this approach to the synthesis of a trimannan branched at C3 and C6, through a combined intramolecular-intermolecular onepot glycosylation with minimal hydroxyl group protection. 4d On the other hand, recent work by Fraser-Reid and coworkers 5b,6 has shown that the, normally overlooked, substituent at O-2 plays an important role in determining the regioselectivity on the glycosylation of diols. In this work we have drawn the attention to the, normally unnoticed, substituents at O-6 and O-3 in a mannoside-2,4-diol. Furthermore, we have compared intramolecular with intermolecular glycosylation processes.The synthesis of mannosides branched at the C2 and C4 positions has been less studied than that of the 6,3-and 6,2-substituted oligomannosaccharides; however, some interesting results regarding regioselectivity have been published. 5 For example, position 4 of acceptors 4a and 4b is glycosylated in a regioselective manner, respectively, by donors 1 and 3, which have participating groups at C2 (Figure 1). 5a In contrast, when donor 2 with a non-participating group is used, the C2 hydroxyl group of the mannose acceptor 4a undergoes complete regioselective glycosylation. 5b It has also been shown that glucosamine donors with phthalimide as the participating protecting group at C2 also react regioselectively with the C4 hydroxyl group of the acceptor. 7The results of our investigations into the regioselectivity of the equivalent reaction in the context of intramolecular glycosylation appeared to complement to those described previously for intermolecular processes and led us to undertake a thorough examination of the factors involved. Figure 1 Regioselective glycosylations of mannoside acceptors 4 and donors with participating (1 and 3) and non-participating (2) groupsWe first investigated the regioselectivity of glycoside donors in reactions with mannose diol acceptors analogous to 4 in an intramolecular glycosylation of diols 5 (Figure 2). The effects of both participating and nonparticipating groups at position C2 of the donors were analyzed. The C6¢ and C3 positions were chosen as the anchoring sites for the donor and acceptor, respectively. In order to analyze th...

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Section: Phenyl 234-tri-o-acetyl-6-o-[methyl-o-(6-o-tertbutyldimethmentioning

confidence: 99%

Study of the Regioselectivity of Intra- and Intermolecular Glycosylations of Mannoside Diol Acceptors

Cid¹,

Valverde²,

López³

et al. 2005

Synlett

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“…The fifth concept for one-pot oligosaccharide synthesis relies on the differentiation between various hydroxyl groups, such as primary versus secondary or equatorial versus axial, have been explored. 426…”

Section: Traditional Manual Synthesis Of Oligosaccharidesmentioning

confidence: 99%

Automated Chemical Oligosaccharide Synthesis: Novel Approach to Traditional Challenges

et al. 2018

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Advances in carbohydrate chemistry have certainly made common oligosaccharides much more accessible. However, many current methods still rely heavily upon specialized knowledge of carbohydrate chemistry. The application of automated technologies to chemical and life science applications such as genomics and proteomics represents a vibrant field. These automated technologies also present opportunities for their application to organic synthesis, including that of the synthesis of oligosaccharides. However, application of automated methods to the synthesis of carbohydrates is an underdeveloped area as compared to other classes of biomolecules. The overarching goal of this review article is to present the advances that have been made at the interface of carbohydrate chemistry and automated technology.

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“…Valverde and co-workers developed a combined intramolecular-intermolecular one-pot glcosylation method [34]. Glycosyl donor 1 was tethered with glycosyl acceptor 2 by phthalic anhydride in the form of acetate.…”

Section: One-pot Reaction With Glycosyl Donors Bearing Same Class Of mentioning

confidence: 99%

Oligosaccharide Synthesis and Library Assembly by One-Pot Sequential Glycosylation Strategy

Wang¹,

Zhang²,

2006

CCHTS

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The oligosaccharide residue in glycoconjugates located in cell membranes is responsible for intercellular recognition and interaction: it acts as a receptor for proteins, hormones, and microorganisms and governs immune reactions. These significant activities have stimulated great interest in the field of oligosaccharides and glycoconjugates. Although many advances have been made in the synthesis of oligosaccharides, more convenient and efficient methods are still needed. This review describes one of these new methods-the one-pot sequential glycosylation approach as a potent tool for oligosaccharide assembly. The oligosaccharide library construction in a one-pot fashion is also summarized.

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A combined intramolecular–intermolecular one-pot glycosylation approach for the synthesis of a branched trisaccharide

Cited by 20 publications

References 34 publications

Study of the Regioselectivity of Intra- and Intermolecular Glycosylations of Mannoside Diol Acceptors

Study of the Regioselectivity of Intra- and Intermolecular Glycosylations of Mannoside Diol Acceptors

Automated Chemical Oligosaccharide Synthesis: Novel Approach to Traditional Challenges

Oligosaccharide Synthesis and Library Assembly by One-Pot Sequential Glycosylation Strategy

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