In Situ Preactivation Strategies for the Expeditious Synthesis of Oligosaccharides: A Review

Bouhall, Samantha K.; Sucheck, Steven J.

doi:10.1080/07328303.2014.931964

Cited by 15 publications

(11 citation statements)

References 68 publications

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“…The concept may look similar to the previously developed two-step 47–49 or preactivation approaches. 50–52 The similarity is undeniable, but there is a key conceptual difference. In two-step or preactivation approaches, glycosyl donor is entirely converted to a reactive intermediate which is then reacted with a glycosyl acceptor.…”

Section: Resultsmentioning

confidence: 99%

Regenerative Glycosylation

et al. 2017

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Previously, we communicated 3,3-difluoroxindole (HOFox)-mediated glycosylations wherein 3,3-difluoro-3H-indol-2-yl (OFox) imidates were found to be key intermediates. Both the in situ synthesis from the corresponding glycosyl bromides and activation of the OFox imidates could be conducted in a regenerative fashion. Herein, we extend this study to the synthesis of various glycosidic linkages using different sugar series. The main outcome of this study relates to enhanced yields and/or reduced reaction times of glycosylations. The effect of HOFox-mediated reactions is particularly pronounced in case of unreactive glycosyl donors and/or glycosyl acceptors. A multistep regenerative synthesis of oligosaccharides is also reported.

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Section: Resultsmentioning

confidence: 99%

Regenerative Glycosylation

et al. 2017

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“…In comparison, the preactivation-based iterative glycosylation is unique, where a glycosyl donor is preactivated in the absence of an acceptor to produce a reactive intermediate ( Scheme 1 ) [ 18 – 21 ]. Upon complete donor activation, the acceptor is added to the reaction mixture, which nucleophilically attacks the intermediate forming the desired glycosidic product [ 22 – 24 ].…”

Section: Reviewmentioning

confidence: 99%

Preactivation-based chemoselective glycosylations: A powerful strategy for oligosaccharide assembly

Yang¹,

Yang²,

Ramadan³

et al. 2017

Beilstein J. Org. Chem.

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Most glycosylation reactions are performed by mixing the glycosyl donor and acceptor together followed by the addition of a promoter. While many oligosaccharides have been synthesized successfully using this premixed strategy, extensive protective group manipulation and aglycon adjustment often need to be performed on oligosaccharide intermediates, which lower the overall synthetic efficiency. Preactivation-based glycosylation refers to strategies where the glycosyl donor is activated by a promoter in the absence of an acceptor. The subsequent acceptor addition then leads to the formation of the glycoside product. As donor activation and glycosylation are carried out in two distinct steps, unique chemoselectivities can be obtained. Successful glycosylation can be performed independent of anomeric reactivities of the building blocks. In addition, one-pot protocols have been developed that have enabled multiple-step glycosylations in the same reaction flask without the need for intermediate purification. Complex glycans containing both 1,2-cis and 1,2-trans linkages, branched oligosaccharides, uronic acids, sialic acids, modifications such as sulfate esters and deoxy glycosides have been successfully synthesized. The preactivation-based chemoselective glycosylation is a powerful strategy for oligosaccharide assembly complementing the more traditional premixed method.

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“…In recent decades, various synthetic methods including onepot synthesis, solid-phase synthesis, cascade multienzymatic synthesis and chemo-enzymatic synthesis, have been wellinvestigated to prepare structurally defined N-glycans (Bartolozzi and Seeberger, 2001;Yu et al, 2005a;Muthana et al, 2009;Kajiwara, 2010;Bouhall and Sucheck, 2014;Yu and Chen, 2016;Kinnaert et al, 2017). However, it is difficult to achieve a general synthetic method for N-glycans due to their complicated structures and inherent chemical properties (Boltje et al, 2009).…”

Section: Introductionmentioning

confidence: 99%

Recent Progress in Chemo-Enzymatic Methods for the Synthesis of N-Glycans

et al. 2020

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Asparagine (N)-linked glycosylation is one of the most common co-and post-translational modifications of both intra-and extracellularly distributing proteins, which directly affects their biological functions, such as protein folding, stability and intercellular traffic. Production of the structural well-defined homogeneous N-glycans contributes to comprehensive investigation of their biological roles and molecular basis. Among the various methods, chemo-enzymatic approach serves as an alternative to chemical synthesis, providing high stereoselectivity and economic efficiency. This review summarizes some recent advances in the chemo-enzymatic methods for the production of N-glycans, including the preparation of substrates and sugar donors, and the progress in the glycosyltransferases characterization which leads to the diversity of N-glycan synthesis. We discuss the bottle-neck and new opportunities in exploiting the chemo-enzymatic synthesis of N-glycans based on our research experiences. In addition, downstream applications of the constructed N-glycans, such as automation devices and homogeneous glycoproteins synthesis are also described.

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In Situ Preactivation Strategies for the Expeditious Synthesis of Oligosaccharides: A Review

Cited by 15 publications

References 68 publications

Regenerative Glycosylation

Regenerative Glycosylation

Preactivation-based chemoselective glycosylations: A powerful strategy for oligosaccharide assembly

Recent Progress in Chemo-Enzymatic Methods for the Synthesis of N-Glycans

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