- A general approach to C-Acyl glycosides via palladium/copper Co-catalyzed coupling reaction of glycosyl carbothioates and arylboronic acids
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A general and efficient approach to the synthesis of various C-acyl glycosides has been developed via Pd2(dba)3/CuTC co-catalyzed cross-coupling reaction of glycosyl carbothioates with arylboronic acids. The reaction showed a broad s
- Wang, Li-Na,Niu, You-Hong,Cai, Qing-Hui,Li, Qin,Ye, Xin-Shan
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- Establishment of Guidelines for the Control of Glycosylation Reactions and Intermediates by Quantitative Assessment of Reactivity
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Stereocontrolled chemical glycosylation remains a major challenge despite vast efforts reported over many decades and so far still mainly relies on trial and error. Now it is shown that the relative reactivity value (RRV) of thioglycosides is an indicator for revealing stereoselectivities according to four types of acceptors. Mechanistic studies show that the reaction is dominated by two distinct intermediates: glycosyl triflates and glycosyl halides from N-halosuccinimide (NXS)/TfOH. The formation of glycosyl halide is highly correlated with the production of α-glycoside. These findings enable glycosylation reactions to be foreseen by using RRVs as an α/β-selectivity indicator and guidelines and rules to be developed for stereocontrolled glycosylation.
- Chang, Chun-Wei,Wu, Chia-Hui,Lin, Mei-Huei,Liao, Pin-Hsuan,Chang, Chun-Chi,Chuang, Hsiao-Han,Lin, Su-Ching,Lam, Sarah,Verma, Ved Prakash,Hsu, Chao-Ping,Wang, Cheng-Chung
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supporting information
p. 16775 - 16779
(2019/11/03)
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- IMPROVED PROCESS FOR PREPARATION OF 2,3,4,6-TETRA-O-BENZYL-D-GALACTOSE
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Provided herein is an improved process for the preparation of benzylated derivative of D-galactose, particularly 2,3,4,6-tetra-O-benzyl-D-galactose that gives higher yield and better purity being cost effective with reduced impurities.
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Page/Page column 25; 26; 27
(2020/01/08)
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- Addition of Organozinc Reagents to Glycopyranosyl Cyanides: Access to Keto Ester-C-glycosides or Unsaturated Acyl-C-glycosides
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Addition of Reformatsky-type or allylic zinc reagents to 2,3,4,6-tetra-O-benzylglycopyranosyl cyanides led to keto ester-C-glycosides or unsaturated acyl-C-glycosides in moderate to excellent yields in the galactose, glucose, and mannose series.
- Ella Obame, Idriss,Ireddy, Prathap,Guisot, Nicolas E. S.,Nourry, Arnaud,Saluzzo, Christine,Dujardin, Gilles,Dubreuil, Didier,Pipelier, Muriel,Guillarme, Stéphane
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p. 1735 - 1738
(2018/04/24)
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- C-GLYCOSIDE COMPOUNDS USEFUL FOR TREATING DISEASE
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The present invention relates to mannoside derivative compounds useful as inhibitors of FimH and methods for the treatment or prevention of urinary tract infection.
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Paragraph 00190; 00191
(2017/10/06)
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- MANNOSE-DERIVED ANTAGONISTS OF FIMH USEFUL FOR TREATING DISEASE
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The present invention relates to mannoside derivative compounds useful as inhibitors of FimH and methods for the treatment or prevention of urinary tract infection.
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Paragraph 0201
(2017/10/13)
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- Monosaccharidic mimetics of the sialyl LewisX tetrasaccharide based on 2,7-dihydroxynaphthalene
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A potential monosaccharidic mimetic of the sialyl LewisX tetrasaccharide (sLeX) was identified based on an in silico docking study using the crystal structure of an E-selectin-sLeX complex. The chemical synthesis of the mimetic in an ortho-selective C-glycosylation is described. This compound and two close analogues were evaluated in a cell-based selectin binding assay where none of the tested mimetics showed an IC 50 below 1mM. This result can be explained by an unexpected 1C4 conformation of the mannosyl residue which precludes the required binding of the Ca2+-ion in E-selectin.
- Weck, Stefan,Frank, Martin,Hamann, Alf,Opatz, Till
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p. 134 - 148
(2013/09/24)
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- Novel glycolipid TLR2 ligands of the type Pam2Cys-α-Gal: Synthesis and biological properties
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A more complete understanding of the mechanism of action of TLR agonists has fueled the investigation of new synthetic immunoadjuvants. In this context, we designed and synthesized glycolipids of the type Pam2Cys-α- Galactose as novel immunoadj
- Thomann, Jean-Sébastien,Monneaux, Fanny,Creusat, Ga?lle,Spanedda, Maria Vittoria,Heurtault, Béatrice,Habermacher, Chloé,Schuber, Francis,Bourel-Bonnet, Line,Frisch, Beno?t
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supporting information; experimental part
p. 174 - 183
(2012/07/14)
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- Synthesis of 1,2,3-triazole linked galactopyranosides and evaluation of cholera toxin inhibition
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We report the synthesis of a series of bivalent 1,2,3-triazole linked galactopyranosides as potential inhibitors of cholera toxin (CT). The inhibitory activity of the bivalent series was examined (ELISA) and the series showed low inhibitory activity (millimolar IC50s). Conversely, the monomeric galactotriazole analogues were strong inhibitors of cholera toxin (IC 50 = 71-75 μM). The Royal Society of Chemistry 2011.
- Leaver, David J.,Dawson, Raymond M.,White, Jonathan M.,Polyzos, Anastasios,Hughes, Andrew B.
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supporting information; experimental part
p. 8465 - 8474
(2012/04/23)
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- Syntheses and biological activities of KRN7000 analogues having aromatic residues in the acyl and backbone chains with varying stereochemistry
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KRN7000 is an important ligand identified for CD1d protein of APC, and KRN7000/CD1d complex can stimulate NKT cells to release a broad range of bioactive cytokines. In an effort to understand the structure-activity relationships, we have carried out synth
- Park, Jeong-Ju,Lee, Ji Hyung,Seo, Kyung-Chang,Bricard, Gabriel,Venkataswamy, Manjunatha M.,Porcelli, Steven A.,Chung, Sung-Kee
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supporting information; scheme or table
p. 814 - 818
(2010/06/16)
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- TOLL-LIKE RECEPTOR 9 AGONISTS
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The present invention provides TLR9 agonists comprising, as an active ingredient, a compound represented by formula (I): (wherein a represents 0 or 1; n represents an integer of 0 to 2; m represents an integer of 0 to 5; X1 and X2 each independently represent a hydrogen atom or hydroxy; Y represents an oxygen atom or a sulfur atom; -Q1-represents -O- or the like; -Q2- represents -O- or the like; -Z- represents -O- or the like; R1, R3 and R4 each independently represent hydroxy or the like; R2 and R5 each independently represent a hydrogen atom, hydroxy or the like; and A represents 6-aminopurin-9-yl or the like) or a pharmaceutically acceptable salt thereof, and the like.
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Page/Page column 42
(2009/02/10)
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- On the synthesis of vinyl and phenyl C-furanosides by stereospecific debenzylative cycloetherification
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Open-chain benzyl-ether-protected polyols in which one of the alcohols is either allylic or benzylic are synthesised by addition of organometallic vinyl or phenyl reagents to benzyl-ether-protected carbohydrate hemiacetals. The diastereoselectivity of add
- Cribiù, Riccardo,Eszter Borbas,Cumpstey, Ian
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experimental part
p. 2022 - 2031
(2009/07/18)
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- Synthesis of D-galactopyranosylphosphonic and (D-galactopyranosylmethyl) phosphonic acids as intermediates of inhibitors of galactosyltransferases
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Employing the Michaelis-Arbuzov reaction of 1-O-acetyl-2,3,4,6-tetra-O- benzyl-D-galactopyranose with triethyl phosphite and trimethylsilyl trifluoromethanesulfonate, α- and β-D-galactopyranosylphosphonic acids were prepared in 33 and 28% yields, respecti
- Heissigerova, Helena,Kocalka, Petr,Hlavackova, Martina,Imberty, Anne,Breton, Christelle,Chazalet, Valerie,Moravcova, Jitka
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p. 1659 - 1672
(2008/09/21)
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- A concise synthesis of (3S,4S,5R)-1-(α-d-galactopyranosyl)-3- tetracosanoylamino-4,5-decanediol, a C-glycoside analogue of immunomodulating α-galactosylceramide OCH
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A concise and convergent synthesis of the C-glycoside analogue 2b of immunomodulating α-galactosylceramide OCH 1b starting from readily available 2,3,4,6-tetra-O-benzyl-d-galactose 3 and l-arabinose 6 is described. The synthesis features the nucleophilic addition of an α-ethynyl sugar 5 to the phytosphingosine-precursor aldehyde 9 and would be applicable to a variety of C-glycoside analogues of interest.
- Toba, Tetsuya,Murata, Kenji,Yamamura, Takashi,Miyake, Sachiko,Annoura, Hirokazu
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p. 5043 - 5047
(2007/10/03)
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- Novel synthetic C-glycolipids, their synthesis and use to treat infections, cancer and autoimmune diseases
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The invention is directed to novel compounds of formulae (I), (II) and (III): wherein X is O or NH; R3 is OH or a monosaccharide and R4 is hydrogen, or R3 is hydrogen and R4 is OH or a monosaccharide; R5 is hydrogen or a monosaccharide; and pharmaceutically acceptable salts or esters thereof. The invention is also directed to the use of the compounds both directly and as immune adjuvants for treating cancer, infectious diseases and autoimmune diseases. The invention is also directed to syntheses of the intermediates which can be used to make these novel compounds.
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- Synthesis of α- and β-glycosyl asparagine ethylene isosteres (C-glycosyl asparagines) via sugar acetylenes and Garner aldehyde coupling
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A convergent approach has been developed for the synthesis of C-glycosyl amino acids in which the glycinyl moiety CH(NH2)CO2H is connected to the anomeric center of the sugar residue by a three carbon atom tether. Essentially, these compounds are isosteres of N-glycosyl asparagines in which the amide group has been replaced by an ethylene bridge. Following the coupling of α- or β-D-linked lithium C-glycoside acetylides with N-Boc D-serinal acetonide (Garner aldehyde), the resulting adducts were transformed into the final N-Boc-C-glycosyl-α-aminopentanoic acids via reduction of the triple bond, deoxygenation, and oxidative cleavage of the oxazolidine ring. By this protocol, 12 C-glycosyl asparagines, six pairs of α- and β-anomers, have been prepared incorporating the gluco, galacto, manno, and the corresponding 2-acetamido-2-deoxy residues.
- Dondoni, Alessandro,Mariotti, Giandomenico,Marra, Alberto
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p. 4475 - 4486
(2007/10/03)
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- 1-O-Acetyl-β-D-galactopyranose: A novel substrate for the transglycosylation reaction catalyzed by the β-galactosidase from Penicillium sp.
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1-O-Acetyl-β-D-galactopyranose (AcGal), a new substrate for β-galactosidase, was synthesized in a stereoselective manner by the trichloroacetimidate procedure. Kinetic parameters (KM and kcat) for the hydrolysis of 1-O-acetyl-β-D-galactopyranose catalyzed by the β-D-galactosidase from Penicillium sp. were compared with similar characteristics for a number of natural and synthetic substrates. The value for kcat in the hydrolysis of AcGal was three orders of magnitude greater than for other known substrates. The β-galactosidase hydrolyzes AcGal with retention of anomeric configuration. The transglycosylation activity of the β-D-galactosidase in the reaction of AcGal and methyl β-D-galactopyranoside (1) as substrates was investigated by 1H NMR spectroscopy and HPLC techniques. The transglycosylation product using AcGal as a substrate was β-D-galactopyranosyl-(1→6)-1-O-acetyl-β-D-galactopyranose (with a yield of ~70%). In the case of 1 as a substrate, the main transglycosylation product was methyl β-D-galactopyranosyl-(1→6)-β-D-galactopyranoside. Methyl β-D-galactopyranosyl-(1→3)-β-D-galactopyranoside was found to be minor product in the latter reaction.
- Zinin, Alexander I.,Eneyskaya, Elena V.,Shabalin, Konstantin A.,Kulminskaya, Anna A.,Shishlyannikov, Sergei M.,Neustroev, Kirill N.
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p. 635 - 642
(2007/10/03)
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- C(2)-(α-Mannosyl)indole: The pivotal intermediate towards the natural C-Glycopeptides
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Two different approaches were investigated to prepare the unusual modified peptide C(2)-mannosylated indole residue. Direct glycosylation of 2-metallated indoles or 2-trimethylsilylindole derivative by reaction with perbenzylated α-D-mannopyranosyl bromid
- Hassan,Spies,Bredenkamp
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p. 1589 - 1598
(2007/10/03)
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- Iodine : A versatile reagent in carbohydrate chemistry IV. Per-O-Acetylation, regioselective acylation and acetolysis
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Iodine has been found to be an effective Lewis acid for promoting the per-O-acetylation of unprotected sugars. Under controlled conditions it can bring about regioselective acylation of carbohydrate derivatives. At higher concentration and with longer reaction times, iodine can effect the selective acetolysis of benzyl ether-protected primary hydroxyl groups. All of these reactions proceed in high yield, are easy to carry out and make use of readily available iodine, which is both cheap and easy to handle.
- Kartha, K. P. Ravindranathan,Field, Robert A.
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p. 11753 - 11766
(2007/10/03)
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- Synthesis of a tetra-and a hexasaccharide donor corresponding to the non-reducing termini of mycobacterial 3-O-methylmannose polysaccharide (MMP)
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The blockwise synthesis of the title compounds, namely the tetra-and the hexasaccharide trichloroacetimidates (20) and (23), is described. Both acetates and imidates were employed as glycosyl donors in most of the coupling reactions. As nearly all of the
- Liao, Wensheng,Lu, Depei,Li, Aihong,Kong, Fanzuo
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p. 877 - 890
(2007/10/03)
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- Anionic Additions to Glycosyl Iodides: Highly Stereoselective Syntheses of β C-, N-, and O-Glycosides
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Classically, glycosyl halides are activated as glycosyl donors by metal chelation under KoenigsKnorr or Helferich conditions. These reactions often proceed through oxonium formation, and the stereochemical outcome is dictated by the anorneric effect and/or the nature of the protecting group on the C2 hydroxyl. Alternatively, glycosyl halides may undergo direct displacement of the halide by an incoming nucleophile in an SN2 mechanism. The latter reaction is far less common, and before this study it was primarily performed with glycosyl bromides. Having recently shown that both α and βglycosyl iodides could be efficiently generated, we embarked upon an investigation of nucleophilic additions to glycosyl iodides. The studies reported herein show that additions of stabilized anions to α-glycosyl iodides proceed with inversion of stereochemistry to give β-glycosides, even in the absence of a C2 participatory group. Glucosyl, galactosyl, and mannosyl iodides were studied, and the combined results indicate that the reactivity of 2,3,4,6-tetra-O-benzyl-α-D-galactosyl iodide > 2,3,4,6-tetra-O-benzyl-α-D-glucosyl iodide > 2,3,4,6-tetra-O-benzyl-α-D-mannosyl iodide. Both the glucosy] and galactosyl iodides are susceptible to E-2 elimination when treated with highly basic anions. In contrast, the mannosyl iodide undergoes substitution to give the 1,2 cis configuration. The overall sequence involves reaction of an anorneric acetate with trimethylsilyl iodide with in vacua removal of the resulting trimethylsilyl acetate. The iodide is then treated with a nucleophile without further characterization. A variety of nucleophiles were stereoselectively added to the glycosyl halides providing β-, C-, N-, and O-glycosides.
- Gervay, Jacquelyn,Hadd, Michael J.
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p. 6961 - 6967
(2007/10/03)
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- Effect of complexation of silver ion with the glycosyl donor and acceptor on the regio- and stereo-selectivity in the β-mannopyranosylation of 1,3-di-N-benzyloxycarbonyl-2-deoxystreptamine using silver triflate as a promoter in tetrahydrofuran
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A pseudodisaccharide, a 5-O-(β-D-mannopyranosyl)-2-deoxystreptamine derivative, was obtained preferentially when 2,3,4-tri-O-allyl-6-O-benzyl-α-D-mannopyranosyl chloride (1) was used as the glycosyl donor for coupling with 1,3-di-N-benzyloxycarbonyl-2-deoxystreptamine (2) using silver triflate as a promoter in tetrahydrofuran.Complexation of the glycosyl acceptor and the allyl protecting group of the glycosyl donor with the promoter proved important for the regio- and stereo-selective formation of the β-mannopyranosyl linkage.
- Tamura, Jun-ichi,Horito, Shigeomi,Yoshimura, Juji,Hashimoto, Hironobu
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p. 153 - 165
(2007/10/02)
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- Synthesis of Glycopyranosylphosphonate Analogues of Certain Natural Nucleoside Diphosphate Sugars as Potential Inhibitors of Glycosyltransferases
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The synthesis of α-D-glucopyranosyl-, α-D-galactopyranosyl-, and α-D-mannopyranosylphosphonate is described.Condensation of tris(trimethylsilyl)phosphite with 2,3,4,6-tetrakis-O-(phenylmethyl)-1-O-acetyl-α-D-glucopyranose generated 2,3,4,6-tetrakis-O-(phe
- Vaghefi, Morteza M.,Bernacki, Ralph J.,Dalley, N. Kent,Wilson, Bruce E.,Robins, Roland K.
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p. 1383 - 1391
(2007/10/02)
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- Synthesis of 1,2-cis-Configurated Glycosylphophonates
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A synthesis of 1,2-cis-configurated, non-isosteric phosphonate analogues of aldose-1-phosphates is described.Treatment of 1-O-acyl-glycose 1, 7, 13, and 19 with trialkyl phosphite in the presence of trimethylsilyl trifluormethanesulfonate gave the 1,2-cis-configurated glycosylphosphonates 2, 4, 8, 10, 14, 16, 20, and 22 as the major anomers and the 1,2-trans-configurated glycosylphosphonates 3, 5, 9, 11, 15, 17, 21 and 23 as the minor anomers.The 1,2-cis-configurated phosphonates 4, 10, 16, and 22 were deprotected to give the (α-D-glucopyranosyl)phosphonate 6, the (β-D-mannopyranosyl)phosphonate 12, the (α-D-ribofuranosyl)phosphonate 18, and the (β-D-arabinofuranosyl)phosphonate 24, respectively, in high yields.The preferred formation of 1,2-cis-configurated phosphonates is explained by postulating an equilibrium between the anomeric phosphonium-salt intermediates (such as 25 and 26) and a stabilization of the cis-configurated salts through formation of pentacoordinated species (such as 28).
- Meuwly, Roger,Vasella, Andrea
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-