Catalytic Stereoselective Glycosidation with Glycosyl Diphenyl Phosphates: Rapid Construction of 1,2‐<i>cis</i>‐α‐Glycosidic Linkages

Koshiba, Miyuki; Suzuki, Noritoshi; Arihara, Ryoichi; Tsuda, Toshifumi; Nambu, Hisanori; Nakamura, Seiichi; Hashimoto, Shinya

doi:10.1002/asia.200800173

Cited by 36 publications

(27 citation statements)

References 137 publications

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“…This result served as the standard for stereoselectivity comparisons. Notably, dioxane belongs to ether coordinating solvents, which have the α‐directing effect . That is, stereochemical results listed in Table originated from a combination of effects of the ether solvent and the remote acyl group at O‐4.…”

Section: Design Of α‐Selective Glycopyranosyl Donors Relying On Remotmentioning

confidence: 99%

Design of α-Selective Glycopyranosyl Donors Relying on Remote Anchimeric Assistance

Komarova

Tsvetkov

Nifantiev

2016

The Chemical Record

107

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Oligosaccharides have a variety of versatile biological effects, but unlike peptides and oligonucleotides, investigation of the roles of oligosaccharides is not easy. Since biosynthesis of oligosaccharides does not comply with direct genetic control, their isolation from natural sources and biotechnological preparation are complicated, due to the heterogeneous composition of raw carbohydrates. Oligosaccharide synthesis is needed for the establishment or confirmation of the structure of natural glycocompounds. Also, synthetically prepared, defined oligosaccharides and their derivatives are becoming increasingly important tools for many biological and immunological research projects. The key step of oligosaccharide synthesis involves glycosylation, a reaction that builds glycosidic bonds. Usually, construction of 1,2-trans-bonds is easy, and therefore, this reaction can even be included into automated syntheses. At this time, installation of the 1,2-cis-bond remains simultaneously frustrating and compelling. In our and other laboratories, a strategy of α-selective (1,2-cis) glycosylation, relying on remote anchimeric assistance with acyl groups, is studied. The state of the art in this work is summarized in this review.

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Section: Design Of α‐Selective Glycopyranosyl Donors Relying On Remotmentioning

confidence: 99%

Design of α-Selective Glycopyranosyl Donors Relying on Remote Anchimeric Assistance

Komarova

Tsvetkov

Nifantiev

2016

The Chemical Record

107

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“…The crude product was purified by silica gel flash column chromatography (5%  10% ethyl acetate in hexanes) to afford product 3 (0.056 mmol, 51.1 mg, 75% yield, 20:1 α:β), the spectroscopic data of which is in good agreement with those reported previously. 6 1 H NMR (500MHz,…”

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confidence: 99%

Selective Synthesis of 1,2-cis-α-Glycosides without Directing Groups. Application to Iterative Oligosaccharide Synthesis

et al. 2013

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A method for the highly selective synthesis of 1,2-cis-α-linked glycosides that does not require the use of the specialized protecting group patterns normally employed to control diastereoselectivity is described. Thioglycoside acceptors can be used, permitting iterative oligosaccharide synthesis. The approach eliminates the need for lengthy syntheses of monosaccharides possessing highly specialized and unconventional protecting group patterns.

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“…Over the past two decades, we have been concerned with the development of novel stereocontrolled glycosidation reactions capitalizing on phosphorus-containing leaving groups (9)(10)(11)(12)(13)(14). (31). In order to demonstrate the synthetic potential of this methodology, we also describe a stereocontrolled synthesis of the α-galactosylceramide KRN7000 (31).…”

Section: A Introductionmentioning

confidence: 99%

Stereocontrolled Construction of 1,2-cis-α-Glycosidic Linkages Using Glycosyl Diphenyl Phosphates and Synthesis of α-Galactosylceramide KRN7000

Nambu

Nakamura

Suzuki

et al. 2010

TIGG

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The development of a general stereoselective method for 1,2-cis-α-glycosidations remains an important issue for synthesis in carbohydrate chemistry. Recently, we have achieved a highly stereocontrolled construction of 1,2-cis-α-glycosidic linkages using glycosyl diphenyl phosphates as glycosyl donors. The per-O-benzyl-protected glucosyl and galactosyl donors and the 3,4,6-tri-O-acetyl-2-azido-2-deoxygalactosyl donor each react with a range of acceptor alcohols in the presence of 0.05-0.2 equiv of HClO 4 in dioxane/Et 2 O (1:1) to afford glycosides in good yields with good to high α-selectivities. The synthetic utility of the present glycosidation method was demonstrated by a stereoselective synthesis of the α-galactosylceramide KRN7000, an activator of natural killer (NK) T cells through CD1d molecules.

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Catalytic Stereoselective Glycosidation with Glycosyl Diphenyl Phosphates: Rapid Construction of 1,2‐cis‐α‐Glycosidic Linkages

Cited by 36 publications

References 137 publications

Design of α-Selective Glycopyranosyl Donors Relying on Remote Anchimeric Assistance

Design of α-Selective Glycopyranosyl Donors Relying on Remote Anchimeric Assistance

Selective Synthesis of 1,2-cis-α-Glycosides without Directing Groups. Application to Iterative Oligosaccharide Synthesis

Stereocontrolled Construction of 1,2-cis-α-Glycosidic Linkages Using Glycosyl Diphenyl Phosphates and Synthesis of α-Galactosylceramide KRN7000

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