On Orthogonal and Selective Activation of Glycosyl Thioimidates and Thioglycosides: Application to Oligosaccharide Assembly

Kaeothip, Sophon; Demchenko, Alexei V.

doi:10.1021/jo201117s

Cited by 26 publications

(22 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To bypass this limitation, Demchenko and co‐workers later introduced S‐thiazolinyl (STaz) glycosides, 76 (Figure ), as building blocks for chemoselective and orthogonal oligosaccharide synthesis . SBox and STaz thioimidates were also implemented in solid ‐ phase glycosylation strategies (Scheme a, b), where the thioimidates were utilized as donors for glycosylations with resin‐bound acceptors after being activated by promoters like AgOTf, TMSOTf, NIS/TMSOTf, MeOTf, and so forth . STaz glycosides proved to be highly stable towards extensive protecting‐group manipulations .…”

Section: Glycosylationsmentioning

confidence: 99%

Chemical O‐Glycosylations: An Overview

2016

View full text Add to dashboard Cite

The development of glycobiology relies on the sources of particular oligosaccharides in their purest forms. As the isolation of the oligosaccharide structures from natural sources is not a reliable option for providing samples with homogeneity, chemical means become pertinent. The growing demand for diverse oligosaccharide structures has prompted the advancement of chemical strategies to stitch sugar molecules with precise stereo‐ and regioselectivity through the formation of glycosidic bonds. This Review will focus on the key developments towards chemical O‐glycosylations in the current century. Synthesis of novel glycosyl donors and acceptors and their unique activation for successful glycosylation are discussed. This Review concludes with a summary of recent developments and comments on future prospects.

show abstract

Section: Glycosylationsmentioning

confidence: 99%

Chemical O‐Glycosylations: An Overview

2016

View full text Add to dashboard Cite

show abstract

“…22 However, aligning multiple leaving groups is not always feasible and syntheses involving sequential activations of three or more different leaving groups are still rare. 23 In this respect, the orthogonal strategy that relies on only two leaving groups that can be orthogonally activated one over another offers a significant advantage. Such activation pathway also requires a pair of orthogonal activators that would activate one, but not the other leaving group.…”

Section: Resultsmentioning

confidence: 99%

S-Benzimidazolyl (SBiz) Imidates as a Platform for Oligosaccharide Synthesis via Active–Latent, Armed–Disarmed, Selective, and Orthogonal Activations

et al. 2017

Self Cite

View full text Add to dashboard Cite

This article describes the development of S-benzimidazolyl (SBiz) imidates as versatile building blocks for oligosaccharide synthesis. The SBiz imidates have been originally developed as a new platform for active-latent glycosylations. This article expands upon the utility of these compounds. The application to practically all common concepts for the expeditious oligosaccharide synthesis including selective, chemoselective, and orthogonal strategies is demonstrated. The strategy development was made possible thanks to our enhanced understanding of the reaction mechanism and the modes by which SBiz imidates interact with various promoters of glycosylation.

show abstract

“…In our recent effort, we developed a selective activation strategy where six different leaving groups could be aligned for the synthesis of hexasaccharide 70 as depicted in Scheme 18 (18). The key to differentiation of these two leaving groups is the choice of activator.…”

Section: Strategies Based On Selective Activationmentioning

confidence: 99%