Acceptor reactivity in glycosylation reactions

Vorm, Stefan van der; Hansen, Thomas; Hengst, Jacob M. A. van; Overkleeft, Herman S.; Marel, Gijsbert A. van der; Codée, Jeroen D. C.

doi:10.1039/c8cs00369f

Cited by 147 publications

(86 citation statements)

References 128 publications

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“…reported that acceptor reactivities were highly related to the stereochemical outcome of chemical glycosylation. [29] However,t he true behavior of na cceptor is hard to depictb ecause its nucleophilicity dependso nn umerous factors, including steric effects, inductive effects, and conformational effects. To gain an insight into the influencing factors of the acceptor,S eeberger et al [5] furthera pplied their automated glycosylation instrument to clarify the relationship between reactivity and stereoselectivity (Table 2).…”

Section: Systematic Studies Related To Glycosylationmentioning

confidence: 99%

Statistical Analysis of Glycosylation Reactions

Chang

Lin

Wang

2020

Chemistry A European J

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Chemical synthesis is one of the practical approaches to access carbohydrate‐based natural products and their derivatives with high quality and in a large quantity. However, stereoselectivity during the glycosylation reaction is the main challenge because the reaction can generate both α‐ and β‐glycosides. The main focus of the present article is the concept of recent mechanistic studies that have applied statistical analysis and quantitation for defining stereoselective changes during the reaction process. Based on experimental evidence, a detailed discussion associated with the mechanism and degree of influence affecting the stereoselective outcome of glycosylation is included.

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Section: Systematic Studies Related To Glycosylationmentioning

confidence: 99%

Statistical Analysis of Glycosylation Reactions

Chang

Lin

Wang

2020

Chemistry A European J

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“…Regioselectivity responds to multiple steric and electronic factors present in both the glycosyl donor and acceptor, and they are characteristic for each particular sugar. Although relative reactivity values have been established for glycosyl donors, it has not been possible to do the same for glycosyl acceptors, whose relative reactivity is still rather poorly understood [6]. Regioselective approaches for the glycosylation of acceptors with more than one free hydroxy group have been developed, and in some of the cases they were successfully rationalized [7][8][9].…”

Section: Introductionmentioning

confidence: 99%

Regioselectivity of glycosylation reactions of galactose acceptors: an experimental and theoretical study

Vigo¹,

Stortz²,

Marino³

2019

Beilstein J. Org. Chem.

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Regioselective glycosylations allow planning simpler strategies for the synthesis of oligosaccharides, and thus reducing the need of using protecting groups. With the idea of gaining further understanding of such regioselectivity, we analyzed the relative reactivity of the OH-3 and OH-4 groups of 2,6-diprotected methyl α- and β-galactopyranoside derivatives in glycosylation reactions. The glycosyl acceptors were efficiently prepared by simple methodologies, and glycosyl donors with different reactivities were assessed. High regioselectivities were achieved in favor of the 1→3 products due to the equatorial orientation of the OH-3 group. A molecular modeling approach endorsed this general trend of favoring O-3 substitution, although it showed some failures to explain subtler factors governing the difference in regioselectivity between some of the acceptors. However, the Galp-(β1→3)-Galp linkage could be regioselectively installed by using some of the acceptors assayed herein.

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“…To address this stereoselectivity problem, we turned our attention to the inuence of glycosyl acceptor reactivity, as acceptor reactivities can signicantly impact stereoselectivities. [53][54][55] Two nucleophiles, i.e., ethanol 8b and tri-uoroethanol (TFE) 8c, were tested (Scheme 2). Glycosylation between 7 and the more reactive acceptor ethanol provided 9b with high yield and b-selectivity (a/b < 1:20), while less reactive acceptor TFE gave a slight preference for the a-anomer product (a/b ¼ 1.6/1).…”

Section: Synthesis Of the Glycosyl Dipeptide Cassettementioning

confidence: 99%