- Practical synthesis of 2-deoxy sugars via metal free deiodination reactions
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2-Deoxy-glycosides, in which the C-2 hydroxyl group is replaced with a hydrogen atom, are important motifs in numerous bioactive natural products and pharmaceutical molecules. Herein, an improved dilauroyl peroxide-mediated radical deiodination reaction b
- Wan, Qian,Wang, Hao,Yao, Wang,Zeng, Jing
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- INHIBITORS OF MALARIAL AND PLASMODIUM FALCIPARUM HEXOSE TRANSPORTER AND USES THEREOF
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Provided are molecules capable of binding to binding pockets of Plasmodium falciparum hexose transporter (PfHT) or analogs thereof and complexes comprising the same. Also provided herein are inhibitors of PfHT, pharmaceutical compositions comprising the i
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Paragraph 00520
(2021/08/14)
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- Direct Deamination of Primary Amines via Isodiazene Intermediates
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We report here a reaction that selectively deaminates primary amines and anilines under mild conditions and with remarkable functional group tolerance including a range of pharmaceutical compounds, amino acids, amino sugars, and natural products. An anomeric amide reagent is uniquely capable of facilitating the reaction through the intermediacy of an unprecedented monosubstituted isodiazene intermediate. In addition to dramatically simplifying deamination compared to existing protocols, our approach enables strategic applications of iminium and amine-directed chemistries as traceless methods. Mechanistic and computational studies support the intermedicacy of a primary isodiazene which exhibits an unexpected divergence from previously studied secondary isodiazenes, leading to cage-escaping, free radical species that engage in a chain, hydrogen-atom transfer process involving aliphatic and diazenyl radical intermediates.
- Berger, Kathleen J.,Driscoll, Julia L.,Yuan, Mingbin,Dherange, Balu D.,Gutierrez, Osvaldo,Levin, Mark D.
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supporting information
p. 17366 - 17373
(2021/11/04)
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- Synthesis method of ginseng saponin new derivative, product produced by synthesis method and application of ginseng saponin new derivative
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The invention relates to a synthesis method of a ginseng saponin new derivative, a product produced by the synthesis method and application of the ginseng saponin new derivative and belongs to the technical field of medicines. The ginseng saponin new derivative is obtained by taking existing ginseng saponin as a raw material and reacting with 2-deoxy-D-glucose; the ginseng saponin new derivative is a medical composition of an active ingredient and can be used as a drug preparation of a crude drug; the ginseng saponin new derivative provided by the invention has relatively strong anti-cancer activity and can be used for preparing drugs for resisting stomach cancer, colon cancer, lung cancer and liver cancer; the ginseng saponin new derivative can be combined with antibacterial drugs including ofloxacin, clindamycin and the like, and has the effects of enhancing the sterilization effect and shortening a disease period; the ginseng saponin new derivative can also be combined with myocardium protection drugs including creatine phosphate sodium, cyclic adenosine monophosphate and the like, so that a myocardium protection effect is enhanced; to sum up, the ginseng saponin new derivative has a very wide application value.
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Paragraph 0081; 0082; 0083
(2017/01/02)
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- Organoboron-catalyzed regio- and stereoselective formation of β-2-deoxyglycosidic linkages
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A borinic acid derived catalyst enables regioselective and β-selective reactions of 2-deoxy- and 2,6-dideoxyglycosyl chloride donors with pyranoside-derived acceptors having unprotected cis-1,2- and 1,3-diol groups. The use of catalysis to promote a β-sel
- Beale, Thomas M.,Moon, Patrick J.,Taylor, Mark S.
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supporting information
p. 3604 - 3607
(2014/07/21)
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- NaBH3CN and other systems as substitutes of tin and silicon hydrides in the light or heat-initiated reduction of halosugars: A tunable access to either 2-deoxy sugars or 1,5-anhydro-itols
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UV light-promoted reduction of acetobromoglucose by NaBH3CN in t-BuOH afforded 1,3,4,6-tetra-O-acetyl-2-deoxy-α-d-arabino-hexopyranose in high yield and purity, via a Surzur-Tanner rearrangement, while, with 10 mol % thiophenol added, acetylated 1,5-anhydro-d-glucitol was cleanly obtained. Such tin-free and mild reductions, presumed to proceed via radical pathways, were more efficient with NaBH3CN compared to NaBH4 or NaBD 4, and do not occur with acetochloroglucose. Similar reductions to 1,3,4,6-tetra-O-acetyl-2-deoxy-α-d-arabino-hexopyranose were achieved upon heating to 80 C t-BuOH or CH3CN solutions of NaBH3CN and AIBN, but with a lower selectivity due to competing ionic reactions. With other pyranosyl bromides, reductions by NaBH3CN could be tuned similarly (d-galacto), but some (d-manno, 5-thio-d-xylo) gave mainly or exclusively 1,5-anhydro-itols. Other conditions, or reagents promoting SET process, afforded also reduced products, but with lower rates or selectivities. Primary iodides were reduced readily with NaBH3CN under UV light.
- Bruyère, Isabelle,Tóth, Zoltan,Benyahia, Hamida,Xue, Jia Lu,Praly, Jean-Pierre
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supporting information
p. 9656 - 9662
(2013/10/22)
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- Direct C-glycosylation of organotrifluoroborates with glycosyl fluorides and its application to the total synthesis of (+)-varitriol
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A mild, stereoselective, and quick approach to accessing alkynyl and alkenyl C-glycosides via BF3?Et2O promoted coupling of organotrifluoroborates and glycosyl fluorides is reported. The application of this method was further demonstrated by the concise and efficient total synthesis of (+)-varitriol in only seven steps.
- Zeng, Jing,Vedachalam, Seenuvasan,Xiang, Shaohua,Liu, Xue-Wei
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supporting information; experimental part
p. 42 - 45
(2011/03/22)
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- DABCO: An efficient promoter for the acetylation of carbohydrates and other substances under solvent-free conditions
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A simple, mild and efficient solvent-free method for the acetylation of carbohydrates, and their partially protected derivatives, as well as non-carbohydrate substances in excellent yields in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) is described with the advantage of tolerance to various functional groups, short reaction time and ease of product isolation.
- Ch, Ratnasekhar,Tyagi, Mohit,Patil, Premanand Ramrao,Kartha, K.P. Ravindranathan
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experimental part
p. 5841 - 5846
(2011/12/03)
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- Erosion of stereochemical control with increasing nucleophilicity: O-glycosylation at the diffusion limit
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(Chemical Equation Presented) Nucleophilic substitution reactions of 2-deoxyglycosyl donors indicated that the reactivity of the oxygen nucleophile has a significant impact on stereoselectivity. Employing ethanol as the nucleophile resulted in a 1:1 (α:β) ratio of diastereomers under SN1-like reaction conditions. Stereoselective formation of the 2-deoxy-α-O-glycoside was only observed when weaker nucleophiles, such as trifluoroethanol, were employed. The lack of stereoselectivity observed in reactions of common oxygen nucleophiles can be attributed to reaction rates of the stereochemistry-determining step that approach the diffusion limit. In this scenario, both faces of the prochiral oxocarbenium ion are subject to nucleophilic addition to afford a statistical mixture of diastereomeric products. Control experiments confirmed that all nucleophilic substitution reactions were performed under kinetic control.
- Beaver, Matthew G.,Woerpel
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supporting information; experimental part
p. 1107 - 1118
(2010/04/06)
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- Five unusual natural carbohydrates from Actinosynnema pretiosum
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Five unusual hexose derivatives were isolated from the carbohydrate portion of the solid-state fermentation extract of Actinosynnema pretiosum ssp. auranticum ATCC 31565, which is a producing strain of maytansinoids that are a family of 19-membered macrocyclic lactams having extraordinary cytotoxic and antineoplastic activities. Their structures were determined to be 2-deoxy-α-D-arabino-hexopyranose (1), 2-deoxy-β-D-arabino- hexopyranose (2), 3,6-anhydro-2-deoxy-α-D-arabino-hexcofuranose (3), 3,6-anhydro-2-deoxy-β-D-arabino-hexofuranose (4), and 2-(D-glycerol-1,2- dihydroxyethyl)furan (5) by NMR spectroscopic experiments. Springer Science+Business Media, Inc. 2008.
- Lu, Chunhua,Bai, Linquan,Shen, Yuemao
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experimental part
p. 594 - 597
(2009/04/07)
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- Hydrolytic reactivity trends among potential prodrugs of the O 2-glycosylated diazeniumdiolate family. Targeting nitric oxide to macrophages for antileishmanial activity
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Glycosylated diazeniumdiolates of structure R2NN(O)=NO-R′ (R′ = a saccharide residue) are potential prodrugs of the nitric oxide (NO)-releasing but acid-sensitive R2NN(O)=NO- ion. Moreover, cleaving the acid-stable glycosides under alkaline conditions provides a convenient protecting group strategy for diazeniumdiolate ions. Here, we report comparative hydrolysis rate data for five representative glycosylated diazeniumdiolates at pH 14, 7.4, and 3.8-4.6 as background for further developing both the protecting group application and the ability to target NO pharmacologically to macrophages harboring intracellular pathogens. Confirming the potential in the latter application, adding R2NN(O)=NO-GlCNAc (where R2N = diethylamino or pyrrolidin-1-yl and GlcNAc = N-acetylglucosamin-1-yl) to cultures of infected mouse macrophages that were deficient in inducible NO synthase caused rapid death of the intracellular protozoan parasite Leishmania major with no host cell toxicity.
- Valdez, Carlos A.,Saavedra, Joseph E.,Showalter, Brett M.,Davies, Keith M.,Wilde, Thomas C.,Citro, Michael L.,Barchi Jr., Joseph J.,Deschamps, Jeffrey R.,Parrish, Damon,El-Gayar, Stefan,Schleicher, Ulrike,Bogdan, Christian,Keefer, Larry K.
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experimental part
p. 3961 - 3970
(2009/05/26)
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- Highly direct α-selective glycosylations of 3,4-o-carbonate-protected 2-deoxy-and 2,6-dideoxythioglycosides by preactivation protocol
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(Chemical Equation Presented) A new efficient pre-activation method for the highly α-stereoselective glycosylation of 2-deoxysugars and 2,6-dideoxysugars has been developed using 2-deoxy- and 2,6- dideoxythioglycosides as glycosyl donors. The approach allows a wide range of glycosyl acceptors and donors to be used; the α-selectivity is very good to excellent.
- Lu, Yin-Suo,Li, Qin,Zhang, Li-He,Ye, Xin-Shan
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supporting information; experimental part
p. 3445 - 3448
(2009/05/07)
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- A method for obtaining equilibrium tautomeric mixtures of reducing sugars via glycosylamines using nonaqueous media
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Equilibrium tautomeric mixtures of several mono- and disaccharides are obtained in anhydrous form, without the use of water, by reacting the commercially available reducing sugars with ammonia gas in dry methanol, followed by the concentration of the resultant solution to dryness. Mutarotation and hydrolysis of the initially formed glycosylamine in the resultant medium account for the transformation. Equilibrium anomeric mixtures enriched in the β-form of commercially available sugars such as α-D-glucose and α-lactose have not only vastly increased solubility, but are also synthetically valuable as these can be readily converted to the methyl/benzyl/trimethylsilyl ether and other derivatives for further transformations.
- Allavudeen, Sikkander Sulthan,Kuberan, Balagurunathan,Loganathan, Duraikkannu
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p. 965 - 968
(2007/10/03)
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- C-Glycosylation of tri-O-benzyl-2-deoxy-D-glucose: Synthesis of naphthyl-substituted 3,6-dioxabicyclo[3.2.2]nonanes
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The syntheses of naphthol 7, naphthol 8, naphthol 11 and naphthol 12 are described, starting from juglone 13. C-Glycosylation of naphthol 8 with benzyl-protected glycosyl donor 10 using trimethylsilyl trifluoromethanesulfonate and silver perchlorate or boron trifluoride-diethyl ether affords rearranged product 36 in which the glycosyl donor has undergone an unusual 1,6-hydride shift. Use of the corresponding naphthol 12 as the glycosyl acceptor under the same conditions affords the expected C-glycoside 34. Use of the naphthol 7 and naphthol 11 affords predominantly rearranged products 35 and 37 respectively, albeit in much lower yield than the reactions using the corresponding bromonaphthols. The study described herein establishes that introduction of an acetyl group to C-3, as in C-glycosylnaphthoquinone 4, as required for conversion to analogues of medermycin 1 such as 3, necessitates that the C-glycosylation step be effected before regioselective introduction of the acetyl group.
- Brimble,Brenstrum
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p. 1612 - 1623
(2007/10/03)
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- Efficient synthesis of 2-deoxyglycosyl-1-O-acyl esters via 2-deoxyglycosyl phosphorodithioates as glycosyl donors
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An efficient glycosylation of carboxylic acids 2a-p has been developed employing 2-deoxyglycosyl phosphorodithioates 1a-h as glycosyl donors and Ag + salts as activators. In the case of aliphatic acids the method is highly β-stereoselective. Stereoselecti
- Borowiecka,Michalska
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p. 709 - 713
(2007/10/02)
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- Synthesis of 2-Deoxy Sugars
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The reduction of acetylated or benzoylated glycosyl halides or selenides with low concentrations of tributylstannane leads to 2-deoxy sugars.An important step in this radical-chain reaction is the cis-selective migration of an ester group.The broad applic
- Giese, Bernd,Gilges, Stefan,Groeninger, Kay S.,Lamberth, Clemens,Witzel, Tom
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p. 615 - 617
(2007/10/02)
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- Reactions of Relevance to the Chemistry of Aminoglycoside Antibiotics. Part 14. A Useful Radical-deamination Reaction
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Primary, secondary, and tertiary aliphatic or alicyclic isocyanides are smoothly reduced under radical conditions using tri-n-butylstannane to the corresponding hydrocarbons.The relative ease of reduction is tertiary > secondary > primary.Aromatic isocyanides are not reduced under these conditions.The reduction of isothiocyanates (or isoselenocyanates) by tri-n-butylstannanae also affords hydrocarbons, but here the isocyanides have been shown to be intermediates.The reduction of a compound with isocyanide and xanthate functions in a 1,2-relationship gives a smooth radical fragmentation to furnish an olefin.An efficient synthesis of 2-deoxy-D-glucose starting with glucosamine is described.
- Barton, Derek H. R.,Bringmann, Gerhard,Lamotte, Genevieve,Motherwell, William B.,Motherwell, Robyn S. Hay,Porter, Alexander E. A.
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p. 2657 - 2664
(2007/10/02)
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