Semisynthesis of Complex-Type Biantennary Oligosaccharides Containing Lactosamine Repeating Units from a Biantennary Oligosaccharide Isolated from a Natural Source

Maki, Yuta; Mima, Takanori; Okamoto, Ryo; Izumi, Masayuki; Kajihara, Yasuhiro

doi:10.1021/acs.joc.7b02485

Cited by 10 publications

(10 citation statements)

References 18 publications

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“…Unfortunately, these methods provide precursors that have several terminal GlcNAc or Gal moieties and therefore cannot be elaborated in a branch selective manner to yield compounds having unique appendages at each antenna. Ingenuous protecting group manipulations have been employed to convert a naturally derived oligosaccharide into glycosyl acceptors that can then be diversified by chemical glycosylation 23,47 . However, this approach involves several low yielding steps and has limited capability to prepare compounds with complex branching patterns.…”

Section: Resultsmentioning

confidence: 99%

Streamlining the chemoenzymatic synthesis of complex N-glycans by a stop and go strategy

et al. 2018

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Contemporary chemoenzymatic approaches can provide highly complex multi-antennary N -linked glycans. These procedures are, however, very demanding and typically involve as many as 100 chemical steps to prepare advanced intermediates that can be diversified by glycosyltransferases in a branch selective manner to give asymmetrical structures commonly found in Nature. Only highly specialized laboratories can perform such syntheses, which greatly hampers progress in glycoscience. Here we describe a biomimetic approach in which a readily available bi-antennary glycopeptide can be converted in 10 or fewer chemical and enzymatic steps into multi-antennary N -glycans that at each arm can be uniquely extended by glycosyltransferases to give access to highly complex asymmetrically branched N -glycans. A key feature of our approach is the installation of additional branching points using recombinant MGAT4 and MGAT5 in combination with unnatural sugar donors. At an appropriate point in the enzymatic synthesis, the unnatural monosaccharides can be converted into their natural counterpart allowing each arm to be elaborated into a unique appendage.

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Section: Resultsmentioning

confidence: 99%

Streamlining the chemoenzymatic synthesis of complex N-glycans by a stop and go strategy

et al. 2018

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“…Based on the established semisynthesis, we can easily access complicated molecules in 10 steps and perform biological studies using the homogeneous substrates. This strategy also enabled us to synthesize a N acetyllactosamine repeated biantennary oligosaccharide 15 and would be useful to prepare various complex type oligosaccharides and glycoproteins.…”

Section: Synthesis Of Triantennary Oligosaccharidesmentioning

confidence: 99%

Studies for Elucidation of Oligosaccharide Functions of Glycoproteins

Maki

Okamoto

Murakami

et al. 2020

J. Synth. Org. Chem. Jpn.

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The attachment of oligosaccharides is one of the most abundant post translational modi cation of proteins. The resultant glycoproteins play central roles in many biological processes. However, the intrinsic heterogeneity of native glycoproteins regarding to the structures of oligosaccharides has hampered the detailed functional studies of the oligosaccharides attached to the proteins. To address this issue, we have been developing chemical methodologies for the synthesis of homogeneous glycoproteins. The chemical approach for the glycoprotein synthesis consists of the preparation of oligosaccharide and glycopeptide building blocks, the assembly of the full length glycopeptides of the target glycoproteins, and folding. This synthetic strategy allowed us to synthesize a variety of structurally de ned forms of glycoproteins.

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“…Sialylglycopeptide (SGP) was also found in hen's egg yolk and digested by PNGase, one of the most highly specific glycosidases extensively used in enzymatic isolation (Seko et al, 1997). Chemical modification of SGP to various other glycoproteins has been developed by Kajihara's group, which achieved semi-synthesis of poly-LacNAc containing complex-type biantennary oligosaccharide (Maki et al, 2017) and was recently applied to triantennary erythropoietin (EPO) N-glycan (Maki et al, 2020).…”

Section: Introductionmentioning

confidence: 99%

Recent Chemical and Chemoenzymatic Strategies to Complex-Type N-Glycans

et al. 2022

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Glycosylation is one of the major forms of protein post-translational modification. N-glycans attached to proteins by covalent bonds play an indispensable role in intercellular interaction and immune function. In human bodies, most of the cell surface glycoproteins and secreted glycopeptides are modified with complex-type N-glycans. Thus, for analytical or medicinal purposes, efficient and universal methods to provide homogeneous complex-type N-glycans have been an urgent need. Despite the extremely complicated structures, tremendous progress in the synthesis of N-glycans has been achieved. On one hand, chemical strategies are shown to be effective to prepare core oligosaccharides of N-glycans by focusing on stereoselective glycosylations such as β-mannosylation and α-sialylation, as well as the methodology of the N-glycan assembly. On the other hand, chemoenzymatic strategies have also become increasingly powerful in recent years. This review attempts to highlight the very recent advancements in chemical and chemoenzymatic strategies for eukaryotic complex-type N-glycans.

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Semisynthesis of Complex-Type Biantennary Oligosaccharides Containing Lactosamine Repeating Units from a Biantennary Oligosaccharide Isolated from a Natural Source

Cited by 10 publications

References 18 publications

Streamlining the chemoenzymatic synthesis of complex N-glycans by a stop and go strategy

Streamlining the chemoenzymatic synthesis of complex N-glycans by a stop and go strategy

Studies for Elucidation of Oligosaccharide Functions of Glycoproteins

Recent Chemical and Chemoenzymatic Strategies to Complex-Type N-Glycans

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