- Cholesteryl glucosides signal through the carbohydrate recognition domain of the macrophage inducible C-type lectin (mincle)
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Cholesteryl α-d-glucosides (αGCs) are unique metabolic products of the cancer-causing human pathogenHelicobacter pylori.Viasignalling through the Macrophage inducible C-type lectin (Mincle) and the induction of a pro-inflammatory response, they are thought to play a role in the development of gastric atrophy. Herein, we prepared the first library of steryld-glucosides and determined that they preferentially signal through the carbohydrate recognition domain of human Mincle, rather than the amino acid consensus motif. Lipidated steryld-glucosides exhibited enhanced Mincle agonist activity, with C18 cholesteryl 6-O-acyl-α-d-glucoside (2c) being the most potent activator of human monocytes. Despite exhibiting strong Mincle signalling, sito- (5b) and stigmasterol glycosides (6b) led to a poor inflammatory response in primary cells, suggesting that Mincle is a potential therapeutic target for preventingH. pylori-mediated inflammation and cancer.
- Timmer, Mattie S. M.,Teunissen, Thomas J.,Kodar, Kristel,Foster, Amy J.,Yamasaki, Sho,Stocker, Bridget L.
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- A Mild Glycosylation Protocol with Glycosyl 1-Methylimidazole-2-carboxylates as Donors
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A mild glycosylation protocol is developed by using glycosyl 1-methylimidazole-2-carboxylates. Such a glycosylation can be promoted by a series of metal triflates and triflimides, especially Cu(OTf)2. The reaction is initiated by activation of
- Chen, Jianpeng,Tang, Yu,Yu, Biao
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p. 4333 - 4344
(2021/07/26)
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- Bismuth(iii) triflate as a novel and efficient activator for glycosyl halides
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Presented herein is the discovery that bismuth(iii) trifluoromethanesulfonate (Bi(OTf)3) is an effective catalyst for the activation of glycosyl bromides and glycosyl chlorides. The key objective for the development of this methodology is to em
- Steber, Hayley B.,Singh, Yashapal,Demchenko, Alexei V.
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p. 3220 - 3233
(2021/04/21)
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- Gold(I)-Catalyzed Glycosylation with Glycosyl Ynenoates as Donors
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A simple and versatile glycosylation method with both armed and disarmed glycosyl ynenoates as donors is developed. Employing a gold(I) complex as catalyst with or without the assistance of TfOH, the scope of the present glycosylation protocol is very wid
- Li, Xiaona,Li, Chenyu,Liu, Rongkun,Wang, Jiazhe,Wang, Zixuan,Chen, Yan,Yang, You
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supporting information
p. 9693 - 9698
(2019/11/29)
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- Gold(I)-Catalyzed Intermolecular Rearrangement Reaction of Glycosyl Alkynoic β-Ketoesters for the Synthesis of 4- O-Glycosylated 2-Pyrones
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A new gold(I)-catalyzed rearrangement reaction with glycosyl alkynoic β-ketoesters as substrates is developed. The rearrangement reactions under the catalysis of PPh3AuOTf proceeded smoothly to afford a range of 4-O-glycosylated 2-pyrones. Base
- Liu, Rongkun,Li, Xiaoqian,Li, Xiaona,Wang, Jiazhe,Yang, You
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p. 14141 - 14150
(2019/10/17)
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- Homogeneous Gold-Catalyzed Glycosylations in Continuous Flow
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The use of versatile alkynyl-building blocks that are activated by gold(I)-catalysis is demonstrated to efficiently generate a variety of glycosides in continuous flow. The application of a continuous flow setting to gold(I)-catalyzed glycosylations enables very short reaction times and excellent control of the reaction conditions.
- Matthies, Stefan,McQuade, D. Tyler,Seeberger, Peter H.
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supporting information
p. 3670 - 3673
(2015/08/18)
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- Photoinduced C-S Bond Cleavage of Thioglycosides and Glycosylation
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A glycosyl coupling reaction via photoinduced direct activation of thioglycosides and subsequent O-glycosylation in the absence of photosensitizer was developed for the first time. This reaction underwent a selectively homolytic cleavage of a C-S bond to generate a glycosyl radical, which was oxidized to an oxacarbenium ion by Cu(OTf)2, and a sequential O-glycosylation. A wide range of glycosides were synthesized in moderate to excellent yield using sugars, amino acids, or cholesterol as the acceptors.
- Mao, Run-Ze,Guo, Fan,Xiong, De-Cai,Li, Qin,Duan, Jinyou,Ye, Xin-Shan
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supporting information
p. 5606 - 5609
(2015/12/01)
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- ortho-(Methyltosylaminoethynyl)benzyl glycosides as new glycosyl donors for latent-active glycosylation
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A new glycosylation protocol employing ortho-(methyltosylaminoethynyl)benzyl glycosides as glycosyl donors and TMSOTf as the catalyst is disclosed. These donors can be readily prepared from the corresponding 'latent' ortho-iodobenzyl glycosides via a Sonogashira coupling, thus providing a new approach for the 'latent-active' synthesis of glycans.
- Chen, Xiaoping,Shen, Dacheng,Wang, Qiaoling,Yang, You,Yu, Biao
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supporting information
p. 13957 - 13960
(2015/09/07)
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- Glycosylation of alcohols using glycosyl boranophosphates as glycosyl donors
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A novel glycosylation that uses glycosyl boranophosphate triesters as glycosyl donors and trityl cation (Tr+) as an activator was developed. Two types of reactions were studied: (1) the boranophosphate triester was activated with TrNTf2 to react with an alcohol and (2) O-trityl ethers worked as both glycosyl acceptors and Tr+ sources. The latter gave better results and the desired O-glycosylation products were rapidly generated and isolated in moderate to good yields.
- Tatsumi, Shiro,Matsumura, Fumiko,Oka, Natsuhisa,Wada, Takeshi
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supporting information
p. 3731 - 3734
(2013/07/05)
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- Studies of S -But-3-ynyl and gem -dimethyl S -But-3-ynyl thioglycoside donors in gold-catalyzed glycosylations
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Gold-catalyzed glycosylation using S-but-3-ynyl and gem-dimethyl S-but-3-ynyl thioglycoside donors has been investigated for the synthesis of various types of complex oligosaccharides. It was found that 2,2-dimethyl S-but-3-ynyl thioglycoside donors are m
- Adhikari, Surya,Li, Xiaohua,Zhu, Jianglong
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p. 336 - 359
(2013/10/08)
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- Characterization of the isochromen-4-yl-gold(I) intermediate in the gold(I)-catalyzed glycosidation of glycosyl ortho-alkynylbenzoates and enhancement of the catalytic efficiency thereof
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Gold standard: The title gold complex (see scheme) was characterized unambiguously as an important intermediate in the title reaction. Protonolysis of this vinyl gold(I) complex was critical for regeneration of the active gold(I) species for the catalytic
- Zhu, Yugen,Yu, Biao
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supporting information; experimental part
p. 8329 - 8332
(2011/10/18)
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- Gold(I)-Catalyzed glycosylation with glycosyl ortho-alkynylbenzoates as donors: General scope and application in the synthesis of a cyclic triterpene saponin
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Glycosyl ortho-alkynylbenzoates have emerged as a new generation of donors for glycosidation under the catalysis of gold(I) complexes such as Ph 3PAuOTf and Ph3PAuNTf2 (Tf= trifluoromethanesulfonate). A wide variety of these donors, including 2-deoxy sugar and sialyl donors, are easily prepared and shelf stable. The glycosidic coupling yields with alcohols are gener-ally excellent; even direct coupling with the poorly nucleophilic amides gives satisfactory yields. Moreover, excellent α-selective glycosylation with a 2-deoxy sugar donor and β-selective sialylation have been realized. Application of the present glycosylation protocol in the efficient synthesis of a cyclic triterpene tetrasaccharide have further demonstrated the versatility and efficacy of this new method, in that a novel chemoselective glycosylation of the carboxylic acid and a new one-pot sequential glycosylation sequence have been implemented.
- Li, Yao,Yang, Xiaoyu,Liu, Yunpeng,Zhu, Cunsheng,Yang, You,Yu, Biao
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experimental part
p. 1871 - 1882
(2010/06/20)
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- An efficient glycosylation protocol with glycosyl ortho-alkynylbenzoates as donors under the catalysis of Ph3PAuOTf
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A new and powerful glycosylation protocol with glycosyl ortho-alkynylbenzoates as donors and Ph3PAuOTf as a promoter is disclosed. The donors are readily available and stable; the glycosidic coupling yields are generally excellent; the promotion system is catalytic, neutral, and orthogonal to the known glycosylation conditions.
- Li, Yao,Yang, You,Yu, Biao
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p. 3604 - 3608
(2008/09/21)
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- Stereoselective glycosylations using benzoylated glucosyl halides with inexpensive promoters
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Reactions of O-benzoylated glucopyranosyl halide (I, Br), isolated or generated in situ from per-benzoylated glucose (8a) and trimethylsilyl halide, with various alcohols were efficiently promoted by zinc halide (Cl, Br) or N-bromosuccinimide with a catal
- Murakami, Teiichi,Sato, Yukari,Shibakami, Motonari
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p. 1297 - 1308
(2008/09/21)
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- Propargyl 1,2-orthoesters as glycosyl donors: stereoselective synthesis of 1,2-trans glycosides and disaccharides
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Propargyl 1,2-orthoesters are identified as glycosyl donors. Various glycosides and disaccharides were synthesized in a stereoselective manner using AuBr3 as the promoter. AuBr3 may activate the alkyne resulting in the formation of a
- Sureshkumar, Gopalsamy,Hotha, Srinivas
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p. 6564 - 6568
(2008/02/12)
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- Silver Triflate. A Mild Alternative Catalyst for Glycosylation Conditions Using Trichloroacetimidates as Glycosyl Donors
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Although trimethylsilyl triflate (TMSOTf) has been widely used to promote glycosyl trichloroacetimidates in oligosaccharide synthesis, silver triflate (AgOTf) was proved to be a mild and in some cases more efficient catalyst in TMSOTf-sensitive glycosylations. Migration and degradation in some specific coupling reactions can be reduced significantly under this alternative glycosylation condition.
- Wei, Guohua,Gu, Guofeng,Du, Yuguo
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p. 385 - 393
(2007/10/03)
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- Tetra-O-benzoylglucosylation: A New 1H Nuclear Magnetic Resonance Method for Determination of the Absolute Configuration of Secondary Alcohols
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A new method for determination of the absolute configuration of secondary alcohols based on the anisotropic effect and glycosylation-induced 1H NMR shifts is described.The tetra-O-benzoyl-β-glucosylation of secondary alcohols induces dramatic shifts in the aglycon 1H NMR peaks.The differences between the proton chemical shifts of the D-glucosylated derivative and the free alcohol (Δδ = δD - δROH) or more significantly between their chemical shifts in the D- and L-glucosylated derivatives (Δδ = δD - δL) are characteristic of the absolute configuration of the secondary chiral alcohol.Furthermore, in most cases the sign of the chemical shift difference of the carbinyl protons correlates with the absolute configuration of their carbons, namely positive or negative Δδ are obtained for (R)- or (S)-carbinyl carbons, respectively.Moreover, this method involves the use of one enantiomer and generally a single derivatization is sufficient.
- Trujillo, Mar,Morales, Ezequiel Q.,Vazquez, Jesus T.
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p. 6637 - 6642
(2007/10/02)
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- A Rapid and Efficient Synthesis of 1,2-trans-β-Linked Glycosides via Benzyl- or Benzoyl-protected Glycopyranosyl Phosphates
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A highly stereocontrolled construction of 1,2-trans-β-glycosidic linkage with or without neighbouring-group participation has been achieved using benzyl- or benzoyl-protected glycopyranosyl phosphates as glycosyl donors in the presence of trimethylsilyl t
- Hashimoto, Shun-ichi,Honda, Takeshi,Ikegami, Shiro
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p. 685 - 687
(2007/10/02)
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- SYNTHESIS OF TRITERPENE AND STEROID GLYCOSIDES
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The glycosylation of cholesterol, β-sitosterol, 28-O-acetylbetulin, and betulin with acylated glycosyl halides in the presence of Hg(OAc)2, Hg(CN)2, CdCO3, Ag2O, Ag2CO3, and HgO + HgBr2 usually gives acylated αβ-glycosides accompanied by acetates, ethers, and bromo and unsaturated derivatives of the initial alcohols.The use of Hg(CN)2 gave mainly β anomers (40-87percent), whereas α anomers preponderated when Hg(OAc)2 was the catalyst.When there was a deficiency of hydrogen halide acceptor and in the presence of the acidic catalyst HgBr2*HBr, the β anomer, produced initially, underwent anomerisation.Cholesteryl α-D-glucopyranoside tetra-acetate (48percent) was obtained by anomerisation of the β anomer.
- Uvarova, Nina I.,Atopkina, Lyubov N.,Elyakov, Georgi B.
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