- Automated Solution-Phase Synthesis of S-Glycosides for the Production of Oligomannopyranoside Derivatives
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Thioglycosides are more resistant to enzymatic hydrolysis than their O-linked counterparts, thereby becoming attractive targets for carbohydrate-based therapeutic development. We report the first development of methods for the site-selective incorporation
- Kern, Mallory K.,Pohl, Nicola L. B.
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- Lithium triflate as a new promoter of glycosylation under neutral conditions
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The glycosyl donors 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl trichloroacetimidate and 3,4,6-tri-O-benzyl-α-D-fucopyranosyl trichloroacetimidate were activated under neutral conditions with a catalytic amount (0.05 equiv) of lithium triflate and reacted w
- Lubineau, Andre,Drouillat, Bruno
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- Design and synthesis of multivalent α-1,2-trimannose-linked bioerodible microparticles for applications in immune response studies of Leishmania major infection
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Leishmaniasis, a neglected tropical disease, currently infects approximately 12 million people worldwide with 1 to 2 million new cases each year in predominately underdeveloped countries. The treatment of the disease is severely underdeveloped due to the
- Rintelmann, Chelsea L.,Grinnage-Pulley, Tara,Ross, Kathleen,Kabotso, Daniel E.K.,Toepp, Angela,Cowell, Anne,Petersen, Christine,Narasimhan, Balaji,Pohl, Nicola
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- Concise Total Synthesis of Peyssonnoside A
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Peyssonnoside A is a marine-derived sulfated diterpenoid glucoside with a unique 5/6/3/6 tetracyclic skeleton with a highly substituted cyclopropane ring deeply embedded into the structure. Herein, we report the first total synthesis of this natural product in a concise, efficient, scalable, and highly diastereoselective fashion. The aglucone peyssonnosol was synthesized in 21% overall yield after 15 steps, featuring a Simmons-Smith cyclopropanation and Mukaiyama hydration, fully controlled by the spatial structure of the substrates.
- Chesnokov, Gleb A.,Gademann, Karl
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- Total Synthesis of Myrmekioside A, a Mono-O-alkyl-diglycosylglycerol from Marine Sponge Myrmekioderma sp.
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Myrmekioside A, which was isolated from the marine sponge Myrmekioderma sp. as a member of the family of natural mono-O-alkyl-diglycosylglycerols, and which has a strong reversion effect on the tumor cell morphology of ras-transformed cells at 5 μg/mL, wa
- Zhang, Jun,Li, Chunxia,Sun, Linlin,Yu, Guangli,Guan, Huashi
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Read Online
- Exploring the Biochemical Foundations of a Successful GLUT1-Targeting Strategy to BNCT: Chemical Synthesis and in Vitro Evaluation of the Entire Positional Isomer Library of ortho-Carboranylmethyl-Bearing Glucoconjugates
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Boron neutron capture therapy (BNCT) is a noninvasive binary therapeutic modality applicable to the treatment of cancers. While BNCT offers a tumor-targeting selectivity that is difficult to match by other means, the last obstacles preventing the full har
- Matovi?, Jelena,J?rvinen, Juulia,Sokka, Iris K.,Imlimthan, Surachet,Raitanen, Jan-Erik,Montaser, Ahmed,Maaheimo, Hannu,Huttunen, Kristiina M.,Per?niemi, Sirpa,Airaksinen, Anu J.,Sarparanta, Mirkka,Johansson, Mikael P.,Rautio, Jarkko,Ekholm, Filip S.
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p. 285 - 304
(2020/12/21)
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- Exploring glycosylation reactions under continuous-flow conditions
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The industrial development of carbohydrate-based drugs is greatly thwarted by the typical challenges inherent in oligosaccharide synthesis. The practical advantages of continuous-flow synthesis in microreactors (high reproducibility, easy scalability, and fast reaction optimization) may offer an effective support to make carbohydrates more attractive targets for drug-discovery processes. Here we report a systematic exploration of the glycosylation reaction carried out under microfluidic conditions. Trichloroacetimidates and thioglycosides have been investigated as glycosyl donors, using both primary and secondary acceptors. Each microfluidic glycosylation has been compared with the corresponding batch reaction, in order to highlight advantages and drawbacks of microreactors technology. As a significant example of multistep continuous-flow synthesis, we also describe the preparation of a trisaccharide by means of two consecutive glycosylations performed in interconnected microreactors.
- Cancogni, Damiano,Lay, Luigi
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p. 2873 - 2878
(2015/01/16)
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- Intramolecular aglycon delivery for (1 → 2)-β-mannosylation: Towards the synthesis of phospholipomannan of Candida albicans
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A high yielding method for 1,2-cis-β-D-mannosylation by intra-molecular aglycon delivery (IAD) through p-methoxy benzyl ether/acetal exchange and phenylsulfoxide donor is reported, along with its application in iterative assembly of antigenic (1 → 2)-β-pe
- Gannedi, Veeranjaneyulu,Ali, Asif,Singh, Parvinder Pal,Vishwakarma, Ram A.
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supporting information
p. 2945 - 2947
(2014/05/06)
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- Total synthesis and absolute configuration of epicoccamide D, a naturally occurring mannosylated 3-acyltetramic acid
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The endofungal metabolite epicoccamide D was synthesised in eighteen steps and 17 % yield as the first member of the family of natural glycotetramic acids. The modular character of the synthesis opens access also to analogues featuring different sugars and spacers. It comprises several high-yielding key steps. The β-D-mannosyl group was introduced by using an α-D-glucosyl imidate donor with subsequent oxidative-reductive epimerisation at C-2′. The pyrrolidine ring was closed quantitatively by a Lacey-Dieckmann condensation of an N-(β-ketoacyl)-N-methyl alaninate. The resulting 3-[ω-(β-D- mannosyl)octadec-2-enoyl]tetramic acid was hydrogenated in the presence of the rhodium catalyst (R,R)-[Rh(Et-DUPHOS)][BF4] to establish the (7S)-stereocentre. This was possible only after blocking the acyltetramic acid as a BF2-chelate to prevent capture of the metal catalyst. We also assigned the hitherto unknown configuration of the natural product as being 5S,7S by comparison of its 13C NMR spectroscopic and optical rotation data with those of our two synthetic 5S,7R/S-diasteromers. Copyright
- Loscher, Sebastian,Schobert, Rainer
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supporting information
p. 10619 - 10624
(2013/08/23)
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- Synthesis of tri- and tetra-mannosides based on sequential one-pot three-component glycosylation reactions
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Expeditious syntheses of tri- and tetra-mannosides were carried out based on sequential one-pot glycosylation strategy. In both of these syntheses TMSOTf activated trichloroacetimidate, the first glycosyl donor, and inexpensive readily accessible trichlor
- Basu, Nabamita,Mukherjee, Mana Mohan,Chaudhury, Aritra,Ghosh, Rina
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p. 1815 - 1820
(2014/01/17)
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- 'Naked' and hydrated conformers of the conserved core pentasaccharide of N-linked glycoproteins and its building blocks
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N-glycosylation of eukaryotic proteins is widespread and vital to survival. The pentasaccharide unit -Man3GlcNAc2- lies at the protein-junction core of all oligosaccharides attached to asparagine side chains during this process. Although its absolute conservation implies an indispensable role, associated perhaps with its structure, its unbiased conformation and the potential modulating role of solvation are unknown; both have now been explored through a combination of synthesis, laser spectroscopy, and computation. The proximal -GlcNAc-GlcNAc- unit acts as a rigid rod, while the central, and unusual, -Man-β-1,4-GlcNAc- linkage is more flexible and is modulated by the distal Man-α-1,3- and Man-α-1,6- branching units. Solvation stiffens the 'rod' but leaves the distal residues flexible, through a β-Man pivot, ensuring anchored projection from the protein shell while allowing flexible interaction of the distal portion of N-glycosylation with bulk water and biomolecular assemblies.
- Barry, Conor S.,Cocinero, Emilio J.,Carcabal, Pierre,Gamblin, David P.,Stanca-Kaposta, E. Cristina,Remmert, Sarah M.,Fernandez-Alonso, Maria C.,Rudic, Svemir,Simons, John P.,Davis, Benjamin G.
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supporting information
p. 16895 - 16903
(2013/12/04)
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- Synthesis of the essential core of the human glycosylphosphatidylinositol (GPI) anchor
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The biological role of GPI anchors is of paramount importance; however, we are still far from fully understanding the structure-function relationship of these molecules. One major limiting factor has been the tiny quantities available from natural sources
- Richichi, Barbara,Luzzatto, Lucio,Notaro, Rosario,Marca, Giancarlo La,Nativi, Cristina
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- Total synthesis of caminoside B, a novel antimicrobial glycolipid isolated from the marine sponge Caminus sphaeroconia
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The first total synthesis of caminoside B, a novel marine antimicrobial glycolipid isolated from the marine sponge Caminus sphaeroconia, was developed. This marine small molecule inhibitor (IC50 = 20 μM) targeting type III secretory pathway of
- Zhang, Zaihong,Zong, Chengli,Song, Gaopeng,Lv, Guokai,Chun, Yuexing,Wang, Peng,Ding, Ning,Li, Yingxia
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experimental part
p. 750 - 760
(2010/06/21)
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- The Glc2Man2-fragment of the N-glycan precursor - A novel ligand for the glycan-binding protein malectin?
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The Glcα(1→3)Glcα(1→3)Manα(1→2)Man tetrasaccharide (Glc2Man2-fragment), a substructure of the natural N-glycan precursor, was synthesized. The interaction of this fragment with the protein malectin, a carbohydrate binding protein localized in the endoplasmatic reticulum, was investigated by 1H15N HSQC experiments and isothermal calorimetry. The chemical shift perturbations of nuclei in the protein's backbone caused by the binding of the Glc 2Man2-fragment to malectin suggest a binding mode like the known ligand nigerose. The Royal Society of Chemistry 2010.
- Mueller, Lisa N.,Muhle-Goll, Claudia,Biskup, Moritz B.
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supporting information; scheme or table
p. 3294 - 3299
(2010/08/21)
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- Synthesis of truncated analogues for studying the process of glycosyl phosphatidylinositol modification
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Figure presented Many eukaryotic proteins are modified with a glycosylphosphatidylinositol (GPI) anchor at their C-termini. This post-translational modification causes these proteins to be noncovalently tethered to the plasma membrane. The synthesis of tr
- John, Franklin,Hendrickson, Tamara L.
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supporting information; experimental part
p. 2080 - 2083
(2010/07/03)
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- Preparation of Thiosugars and Their Use
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A process for the preparation of a thiosaccharide represented by Saccharide-S-H wherein Saccharide comprises at least 4 sugar units, comprises subjecting a corresponding compound of the formula (P)Saccharide-S-(P) wherein (P) represents an O- or S-protecting group(s), to Birch reduction.
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Page/Page column 18
(2009/07/18)
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- Solid-phase oligosaccharide synthesis of a small library of N-glycans
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Solid-phase oligosaccharide synthesis is based on a hydroxymethyl-benzyl benzoate spacer linker which is connected to the Merrifield resin (1P). Glycosylation was performed with O-glycosyl trichloroacetimidates of glucosamine, mannose, and galactose permi
- Jonke, Simon,Liu, Ke-Gang,Schmidt, Richard R.
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p. 1274 - 1290
(2008/09/18)
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- Total synthesis of phosphatidylinositol mannosides of Mycobacterium tuberculosis
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The total synthesis of phosphatidylinositol mannosides (PIMs), a key class of antigenic glycolipids found on the cell wall of Mycobacterium tuberculosis, is described. The synthetic strategy relied on a [4 + 3] glycosylation of tetramannoside 1 and pseudo
- Liu, Xinyu,Stocker, Bridget L.,Seeberger, Peter H.
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p. 3638 - 3648
(2007/10/03)
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- Total synthesis of woodrosin I - Part 1: Preparation of the building blocks and evaluation of the glycosylation strategy
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The preparation of three building blocks required for the total synthesis of woodrosin I (1) is outlined, a complex resin glycoside bearing a macrolide ring which spans four of the five sugars of its oligosaccharide backbone. Key steps involve the enantio
- Fuerstner, Alois,Jeanjean, Fabien,Razon, Patrick,Wirtz, Conny,Mynott, Richard
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p. 307 - 319
(2007/10/03)
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- Glycosyl phosphatidylinositol (GPI) anchor synthesis based on versatile building blocks - Total synthesis of a GPI anchor of yeast
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For the design of a synthesis of target molecule 1 the retrosynthetic analysis yielded building blocks 2-5, of which ceramide 2-phosphite derivative 2 and aminoethyl phosphite derivative 5 are known. The generation of α-glucosaminyl (1→6)inositol building
- Mayer, Thomas G.,Schmidt, Richard R.
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p. 1153 - 1165
(2007/10/03)
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- A practical synthesis of β-D-mannopyranosides
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An indirect yet highly efficient protocol for the β-D-mannosylation of sterically hindered alcohols is reported. Trichloroacetimidate 5 is used a key building block which is converted into the desired mannosides 9 via triflates 8 by an ultrasound promoted
- Fuerstner, Alois,Konetzki, Ingo
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p. 5721 - 5724
(2007/10/03)
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- Synthesis and evaluation of thio-trisaccharides as acceptors for N-acetylglucosaminyltransferase-V
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N-Acetylglucosaminyltransferase-V (GlcNAcT-V) transfers a β-linked GlcNAc residue from UDP-GlcNAc to the 6-OH group of the αMan residue in oligosaccharides terminating in the sequence β-D-GlcpNAc-(1→2)-α-D-Manp-(1→6)-β-D-Glcp-OR (5, R = (CH2)s
- Lu,Hindsgaul,Li,Palcic
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p. 790 - 800
(2007/10/03)
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- Synthesis and growth inhibitory properties of glycosides of 1-O- hexadecyl-2-O-methyl-sn-glycerol, analogs of the antitumor ether lipid ET- 18-OCH3 (edelfosine)
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Glycosylated antitumor ether lipids (GAELs), analogs of 1-O-octadecyl- 2-O-methyl-sn-glycero-3-phosphocholine (1, ET-18-OCH3, edelfosine), were synthesized in good overall yields by glycosylation of 1-O-alkyl-2-O- methyl-sn-glycerol and tested for in vitro antineoplastic activity against a variety of murine and human tumor cell lines. Stereospecific glycosylation was achieved by the use of 2-O-acetyl-3,4,6-tri-O-benzylglucopyranosyl and - mannopyranosyl trichloroacetimidates as donors, with trimethylsilyl trifluoromethanesulfonate as catalyst in the presence of molecular sieves at -78 °C. The GAELs differ from 1 in having the sn-3-phosphocholine residue replaced by one of the following monosaccharide residues: β- and α-2- deoxy-D-arabino-hexopyranosyl, α-D-mannopyranosyl, 2-O-methyl-β-D- glucopyranosyl, and 2-O-methyl-α-D-mannopyranosyl. 1-O-Hexadecyl-2-O- methyl-3-O-(2'-deoxy-β-D-arabino-hexopyranosyl)-sn-glycerol (2) was more effective than 1 in inhibiting the growth of MCF-7 (human breast cancer) and its adriamycin-resistant form MCF-7/adriamycin, and murine Lewis lung cancer cells. 2-Deoxy-β-D-arabino-hexopyranoside 2 was also an effective growth inhibitor of two drug-resistant leukemic cell lines, P388/Adr and L1210/vmdr.
- Marino-Albernas, José R.,Bittman, Robert,Peters, Andrew,Mayhew, Eric
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p. 3241 - 3247
(2007/10/03)
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- ONE-POT SYNTHESIS OF SUBSTITUTED ALLYL-α-D-GLUCOPYRANOSIDES BY AN in situ ANOMERIZATION PROTOCOL
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A new 3-step, 1-pot procedure for the stereoselective α-glycosylation of substituted allylic alcohols has been developed.The key step involves an in situ anomerization of the β-glycoside, obtained by Schmidt's glycosylation method, upon treatment with TiCl4.
- Charette, Andre B.,Turcotte, Nathalie,Cote, Bernard
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p. 421 - 432
(2007/10/02)
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- The synthesis of partial structures of complex N-glycoproteins
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Comparable syntheses of β-D-GlcpNAc-(1→2)-[β-D-GlcpNAc-(1→6)]-α-D-Manp-(1→6)-β-D-ManpO (CH2)8CO2Me and β-D-GlcpNAc-(1→2)-α-D-Manp-(1→3)-β-D-ManpO(CH2)8CO2Me with the glycosyl halide and imi
- Paulsen,Helpap
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p. 289 - 313
(2007/10/02)
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- Synthesis of α-D-Manp-(1->3)-4)>-6)>-β-D-Manp-(1->4)-β-D-GlcpNAc-(1->4)-6)>-D-GlcpNAc, a core glycoheptaose of a "bisected" complex-type glycan of glycoproteins
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A synthesis of α-D-Manp-(1->3)-4)>-6)>-β-D-Manp-(1->4)-β-D-GlcpNAc-(1->4)-6)>-D-GlcpNAc was achieved by employing benzyl O-(3,4,6-tri-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl)-(1->4)-O-(2-O-benzyl-β-D-
- Yamazaki, Fumito,Sato, Susumu,Nukada, Tomoo,Ito, Yukishige,Ogawa, Tomoya
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- O-Glycosyl Imidates, 29. - Reaction of O-(Glucopyranosyl)Imidates with Electron-Rich Heterocycles. - Synthesis of C-Glucosides
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The O-benzyl-protected α-glucosyl trichloroacetimidate 1 gives with furan and derivatives and ZnCl2-OEt2 as catalyst via 2-C attack the α-C-glucosides 2-α - 4-α.Good results in this reaction are also obtained with the aryl-substituted glucosyl imidate 5 a
- Schmidt, Richard R.,Effenberger, Gunther
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p. 825 - 832
(2007/10/02)
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