2-Allylphenyl glycosides as complementary building blocks for oligosaccharide and glycoconjugate synthesis

Premathilake, Hemali D.; Demchenko, Alexei V.

doi:10.3762/bjoc.8.66

Cited by 20 publications

(13 citation statements)

References 46 publications

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“…Under such circumstances, a new type of glycosyl donors which can maintain the merits while overcoming the defects of thioglycosides is highly desirable. Based on alkyne-functionality activation with the combination of NIS/TMSOTf, , a new type of phenyl O -glycoside donor, o -( p -methoxyphenylethynyl)phenyl (MPEP) glycoside, was discovered . The new glycosylation donors were so stable that they could be stored at room temperature for at least 6 months without noticeable decomposition.…”

Section: Introductionmentioning

confidence: 99%

o-(p-Methoxyphenylethynyl)phenyl Glycosides: Versatile New Glycosylation Donors for the Highly Efficient Construction of Glycosidic Linkages

Shi

et al. 2017

J. Am. Chem. Soc.

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A novel alkyne-activation-based glycosylation protocol using o-(p-methoxyphenylethynyl)phenyl (MPEP) glycoside was established. The glycosyl MPEP donors were shelf-stable and could be prepared efficiently via Sonogashira reaction from the corresponding o-iodophenyl (IP) glycosides. The outstanding stability of IP glycosides as well as their efficient transformations to MPEP glycosides dramatically facilitates the syntheses of MPEP glycosyl donors and IP glycosyl acceptors. Furthermore, they make the MPEP glycosylation protocol applicable to the latent-active oligosaccharide and glycoconjugate synthetic strategy, with IP glycosides as the latent form and MPEP glycosides as the active form, as illustrated by the highly efficient fabrication of Streptococcus pneumoniae type 3 trisaccharide. The phenolic glycoside nature of MPEP glycosides bestows on the new glycosyl donors enhanced stability compared to their thioglycoside counterparts toward activation conditions applied for glycosyl trichloroacetimidate (TCAI) and o-alkynylbenzoate (ABz) donor. Thus, MPEPs can also be utilized in the selective one-pot glycosylation strategy, as exemplified by the syntheses of oligosaccharides via successive glycosylations with glycosyl TCAI, ABz, and EPMP as donors. Despite sharing identical promotion conditions with thioglycoside donors, the odor-free starting material (IP), the stable departure structure of the leaving group (3-iodobenzofuran), and the decreased nucleophilicity of the o-MPEP glycoside help to eliminate the three major shortcomings of the thioglycoside donors (unpleasant odor of starting material, detrimental interference of the cleaved leaving group, and aglycon intra- or intermolecular migration) while maintaining the prominent features of the thioglycoside methodology, including the broad substrate scopes, the mild promotion conditions, the stability of glycosyl donors, and the versatile applications in existing glycoside synthesis strategies. Based on the experimental results, a mechanism for MPEP activation was proposed, which was supported by systematic mechanistic investigations, including trapping of active intermediates, design of a vital disarmed rhamnosyl donor, and isolation and characterization of the departure species of the leaving group.

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Section: Introductionmentioning

confidence: 99%

o-(p-Methoxyphenylethynyl)phenyl Glycosides: Versatile New Glycosylation Donors for the Highly Efficient Construction of Glycosidic Linkages

Shi

et al. 2017

J. Am. Chem. Soc.

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“…The 4- n -pentenyl glycosides (NPGs, Figure , compd 1 ), introduced by Fraser-Reid, are one of the most important dual donors due to their convenient preparation and versatile applications. To date, more than 100 relevant papers and several modified NPG-type versions, such as gem-dimethyl analogs (developed by the Andrade’s group; Figure , compds 2 and 3 ) and 2-allyloxyphenyl donors (developed by the Hung’s group and Demchenko’s group; Figure , compd 4 ), have been reported. Despite remarkable advances, the NPG(-type) methods still suffer from some limitations.…”

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confidence: 99%

n-Pentenyl-Type Glycosides for Catalytic Glycosylation and Their Application in Single-Catalyst One-Pot Oligosaccharide Assemblies

Sheng

Cheng

et al. 2019

Org. Lett.

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We have developed a new type of n-pentenyl-type glycosides that can be activated by catalytic amounts of promoter, Hg(NTf2)2 or PPh3AuCl/AgNTf2, at room temperature. The mild activation conditions and outstanding stability of common protection/deprotection manipulations enable the enynyl donors to have broad applications in constructing various glycosidic bonds. Furthermore, under the Hg(NTf2)2-catalyzed conditions, the sequential activation of different types of donors was achieved, based on which a gentiotetrasaccharide was synthesized via the newly developed single-catalyst one-pot strategy.

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“…Conceptually, this approach is one of the most effective strategies for expeditious oligosaccharide synthesis. − Yet this strategy remains somewhat underdeveloped with too few known examples to become universally applicable. Only the following examples are known to date: the original S -phenyl vs fluoride introduced by Kanie et al, ,, thioimidate-based approaches developed in our lab, ,− Hotha’s O -pentenyl vs O -propargyl, and O -allylphenyl-based approach also introduced by our group . Likewise, we reported a related, albeit less flexible, semiorthogonal approach using S -ethyl vs O -pentenyl, which was extended to fluoride vs O -pentenyl by Fraser-Reid and Lopez …”

Section: Resultsmentioning

confidence: 88%

“…Only the following examples are known to date: the original S -phenyl vs fluoride introduced by Kanie et al, 24,25,28 thioimidate-based approaches developed in our lab, 19,29–31 Hotha’s O -pentenyl vs O -propargyl, 32 and O -allylphenyl-based approach also introduced by our group. 33 Likewise, we reported a related, albeit less flexible, semiorthogonal approach using S -ethyl vs O -pentenyl, 34 which was extended to fluoride vs O -pentenyl by Fraser-Reid and Lopez. 35 …”

Section: Resultsmentioning

confidence: 99%

“…Only the following examples are known to date: the original S-phenyl vs fluoride introduced by Kanie et al, 24,25,28 thioimidate-based approaches developed in our lab, 19,29−31 Hotha's O-pentenyl vs O-propargyl, 32 and O-allylphenyl-based approach also introduced by our group. 33 Likewise, we reported a related, albeit less flexible, semiorthogonal approach using Sethyl vs O-pentenyl, 34 which was extended to fluoride vs Opentenyl by Fraser-Reid and Lopez. 35 Hence, the subsequent study of this unusual reactivity of SBiz glycosyl donors and their substituted analogues has focused on MeI and DMTST, promoters that showed the greatest difference in the activation profile.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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

et al. 2017

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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.

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2-Allylphenyl glycosides as complementary building blocks for oligosaccharide and glycoconjugate synthesis

Cited by 20 publications

References 46 publications

o-(p-Methoxyphenylethynyl)phenyl Glycosides: Versatile New Glycosylation Donors for the Highly Efficient Construction of Glycosidic Linkages

o-(p-Methoxyphenylethynyl)phenyl Glycosides: Versatile New Glycosylation Donors for the Highly Efficient Construction of Glycosidic Linkages

n-Pentenyl-Type Glycosides for Catalytic Glycosylation and Their Application in Single-Catalyst One-Pot Oligosaccharide Assemblies

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

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