20880-92-6Relevant articles and documents
Preparation of enantiomerically pure fructose-derived 1,3-oxazin-2-one by INIR methodology and its application as a chiral auxiliary in some model asymmetric reactions
Banks, Malcolm R.,Cadogan,Gosney, Ian,Gould, Robert O.,Hodgson, Philip K. G.,McDougall, Douglas
, p. 9765 - 9784 (1998)
A newly developed fructose-based homochiral 1,3-oxazin-2-one reagent prepared via a regioselective and stereoselective intramolecular nitrene insertion reaction (INIR) exerts smooth stereocontrol resulting in high levels of asymmetric induction and chemical yield in various synthetic transformations including aldol, Diels-Alder cycloaddition and α-bromination reactions.
2,3:4,5-DI-O-isopropylidene-β-D-fructopyranose as chiral auxiliary in asymmetric α-alkylation of ester enolates
Costa, Paulo R.R.,Ferreira, Vitor F.,Alencar, Karla G.,Filho, Hiran C.A.,Ferreira, Claudio M.,Pinheiro, Sergio
, p. 691 - 699 (1996)
The asymmetric α-alkylation of enolates of chiral esters derived from 2,3:4,5-di-O-isopropylidene-β-D-fructopyranose (1) was studied. The diastereoselectivities range from 1:1 to 7:3. The absolute stereochemistry of the major S-isomers were established by chemical correlation. The diastereoselectivities of the alkylated products were similar to those observed in the deprotonation steps. The stereochemical outcome can be interpreted by an intramolecular complexation of the lithium cation of the carbohydrate ester enolates.
Structure-sweetness relationships for fructose analogs. Part I. Synthesis and evaluation of sweetness of 5-deoxy-D-threo-hexulose
Martin, Olivier R.,Korppi-Tommola, Sirkka-Liisa,Szarek, Walter A.
, p. 1857 - 1862 (1982)
5-Deoxy-D-threo-hexulose ("5-deoxyfructose", "5-deoxysorbose") has been prepared in six steps from D-fructose.The reaction of 2,3-O-isopropylidene-β-D-fructopyranose with sulfuryl chloride afforded exclusively 5-chloro-5-deoxy-2,3-O-isopropylidene-α-L-sorbopyranose in the key step. "5-Deoxyfructose" exists only in the 2C5(D) pyranoid form in solution, and was found to be much sweeter than L-sorbose and nearly as sweet as D-fructose.Comments on this unexpected sweetness result are given.
Synthesis and sensory characterization of novel umami-tasting glutamate glycoconjugates
Beksan, Ersan,Schieberle, Peter,Robert, Fabien,Blank, Imre,Fay, Laurent Bernard,Schlichtherle-Cerny, Hedwig,Hofmann, Homas
, p. 5428 - 5436 (2003)
Two glycoconjugates of glutamic acid, namely, the N-glycoside dipotassium N-(D-glucos-1-yl)-L-glutamate (1) and the corresponding Amadori compound N-(1-deoxy-D-fructos-1-yl)-L-glutamic acid (2), have been synthesized in yields of 35 and 52%, respectively, using new Maillard-mimetic approaches, and their chemical structures have unequivocally been elucidated by 1D- and 2D-NMR and MS experiments. Systematic sensory studies revealed that both glycoconjugates exhibit pronounced umami-like taste with recognition taste thresholds of 1-2 mmol/L, close to that of monosodium glutamate (MSG). Contrary to an aqueous solution of MSG, 1 does not show the sweetish and slightly soapy by-note, but evokes an intense umami taste. Aqueous solutions of 2 were described by the descriptors umami, seasoning, and bouillon-like. Added to a bouillon base, which did not contain any taste enhancers, both glycoconjugates imparted a distinct umami character similar to the control sample containing the same amount of MSG on a molar basis. To the best of our knowledge, these types of glycoconjugates in general and, in particular, N-glucosyl glutamate and N-deoxyfructosyl glutamate have never been reported as taste active compounds having umami-like properties. Therefore, 1 and 2 represent a new class of umami-type taste compounds showing properties similar to the umami reference compound MSG. Systematic 13C NMR measurements revealed that 1 was fairly stable in aqueous solutions under alkaline conditions (pH 8-10) as well as in dry form. However, it rapidly hydrolyzes in neutral and acidic solutions, giving rise to glucose and glutamate. In contrast, glycoconjugate 2 was observed to be rather stable in aqueous solution as well as in the presence of human saliva.
Biodegradable Glycopolymeric Micelles Obtained by RAFT-controlled Radical Ring-Opening Polymerization
Ganda, Sylvia,Jiang, Yanyan,Thomas, Donald S.,Eliezar, Jeaniffer,Stenzel, Martina H.
, p. 4136 - 4146 (2016)
The design and synthesis of an entirely degradable glycopolymer micelle was presented. This design relies on the utilization of RAFT-controlled radical ring-opening polymerization (rROP) technique to afford multiple insertions of cleavable ester linkages onto the backbone of the corona. RAFT polymerization using a macroRAFT agent based on poly(μ-caprolactone) PCL was employed to control the polymerization of well-defined statistical glycopolymers of 1-O-acryloyl-2,3:4,5-di-O-isopropylidene-β-d-fructopyranose (1-O-AiPrFru) and 5,6-benzo-2-methylene-1,3-dioxepane (BMDO) monomer. Three block copolymers were synthesized to generate poly(μ-caprolactone)-b-poly[(1-O-acryloyl-2,3:4,5-di-O-isopropylidene-β-d-fructopyranose)-co-(5,6-benzo-2-methylene-1,3-dioxepane)] (PCL-b-P[(1-O-AiPrFru)-co-(BMDO)]) with varying block lengths. Self-assembly of the deprotected block copolymers generated nonspherical egg shaped micelles, where the shorter chains PCL106-b-P[(1-O-AFru)69-co-(BMDO)9] underwent self-assembly forming micelles with the hydrodynamic diameter (DH) of 106 nm. The biodegradation of these micelles were investigated via enzymatic degradation by Lipase Pseudomonas sp., indicating entirely degradable architectures, which are no longer visible via dynamic light scattering (DLS). SEC further confirmed the appearance of fragmented glycopolymeric units. In vitro cell proliferation assay of the micelles and their degradation products revealed no toxicity against healthy human fibroblast HS27 and breast cancer MDA-MB-231 cell lines. The polymer concentration range tested was up to 0.20 mg·mL-1 with the cell viabilities of ≥95%.
Enhanced Antimetastatic Activity of the Ruthenium Anticancer Drug RAPTA-C Delivered in Fructose-Coated Micelles
Lu, Mingxia,Chen, Fan,Noy, Janina-Miriam,Lu, Hongxu,Stenzel, Martina H.
, (2017)
The ruthenium complex—dichlororuthenium (II) (p-cymene) (1,3,5-triaza-7-phosphaadamantane) (RAPTA-C)—has shown to be remarkably effective at suppressing the growth of solid tumor metastases. However, poor delivery efficacy and the lack of targeting ability of the common drug delivery system pose significant obstacles to maximize the therapeutic benefit of RAPTA-C. Inspired by the overexpression of GLUT5 transporter on the surface of breast cancer tissues but not the healthy mammary tissues, the use of d-fructose as the targeting moiety of the drug carrier can significantly improve the cellular uptake of nanoparticles, thus further enhancing the therapeutic efficiency of RAPTA-C. In this work, fructose-micelles and 2-hydroxyethyl acrylate (HEA)-micelles are prepared to investigate the difference in cellular uptake. It is found that glycopolymer leads to an increased uptake by breast cancer cells, while the HEA-micelles show less uptake. This behavior is also reflected by the slightly faster movement of fructose-coated micelles in MCF-7 tumor spheroid models using light sheet microscopy as analytical tool. The incorporation of RAPTA-C into micelles can enhance the inhibitory effect of the ruthenium drug demonstrated using invasion, chemotaxis, and haptotaxis assays. As a result, fructose-coated nanoparticles can be a promising drug delivery platform of RAPTA-C for the treatment of metastatic breast cancer. (Figure presented.).
Lipase-catalyzed esterification of steric hindered fructose derivative by continuous flow and batch conditions
Sutili, Felipe K.,Ruela, Halliny S.,Leite, Selma G.F.,Miranda, Leandro S. De M.,Leal, Ivana C.R.,De Souza, Rodrigo O.M.A.
, p. 37 - 42 (2013)
The lipase catalyzed sugar ester synthesis is an interesting strategy for producing biodegradable, non-ionic surfactants. The main disadvantage of this protocol is the long reaction time required for achieving moderated to good yields. Here, we report the esterification of steric hindered fructose derivative where important variables for batch conditions were identified by the use of a RSM protocol and then translated to the continuous flow regime with high conversions and short residence times.
Synthesis and biological evaluation of some 6-substituted purines
Braga, Fernanda Gambogi,Coimbra, Elaine Soares,de Oliveira Matos, Magnum,Lino Carmo, Arturene Maria,Cancio, Marisa Damato,da Silva, Adilson David
, p. 530 - 537 (2007)
We report herein the synthesis and the in vitro antileishmanial evaluation of a series of 6-substituted purines. The most active compounds against Leishmania amazonensis promastigotes were 6-(3′-chloropropylthio)purine 2 (D.A. Benson, I. Karsch-Mizrachi, D.J. Lipman, J. Ostell, B.A. Rapp, D.L. Wheeler, Genbank. Nucleic Acids Res. 28 (2000) 15-18; E.V. Aleksandrova, P.M.I.E. Valashek, J. Med. Pharm. Chem. 35 (2001) 172-173), 6-(3′-(thioethylamine)propylthio)purine 5, 6-(α-aceticacidthio)purine 7 and 6-(6′-deoxy-1′-O-methyl-β-d-ribofuranose)purine 14 with an IC50 = 50, 50, 39 and 29 μM, respectively.
A mild acetolysis procedure for the regioselective removal of isopropylidene in di-O-isopropylidene-protected pyranoside systems
Zhang, Pengfei,Ling, Chang-Chun
, p. 7 - 13 (2017)
A mild acetolysis method for the regioselective removal of isopropylidene group from di-O-isopropylidene-protected hexopyranosides is reported. O-Isopropylidene-protected intermediates play an important role in carbohydrate chemistry, as they are often found in commercially available furanosyl and pyranosyl materials, and some of them contain more than one O-isopropylidene groups. Methods that permit regioselective removal of O-isopropylidene groups are extremely valuable, as the number of steps in the total synthesis of complex oligosaccharides could be significantly decreased. Here we report that trifluoroacetic acid (TFA)/acetic anhydride (Ac2O) can be used to regioselectively convert one of the two O-isopropylidene groups to vicinal di-O-acetates in the di-O-isopropylidene-protected galacto- and fructo-pyranosyl systems, and the reagent is compatible with some common functionalities such as sulfonate esters, bromide, azide etc.
Radiolabeling and in vitro evaluation of a new 5-fluorouracil derivative with cell culture studies
Ilem-Ozdemir, Derya,Atlihan-Gundogdu, Evren,Ekinci, Meliha,Halay, Erkan,Ay, Kadir,Karayildirim, Tamer,Asikoglu, Makbule
, p. 874 - 884 (2019)
The clinical impact and accessibility of 99mTc tracers for cancer diagnosis would be greatly enhanced by the availability of a new, simple, and easy labeling process and radiopharmaceuticals. 5-Fluorouracil is an antitumor drug, which has played an important role for the treatment of breast carcinoma. In the present study, a new derivative of 5-Fluorouracil was synthesized as (1-[{1′-(1′′-deoxy-2′′,3′′:4′′,5′′-di-O-isopropylidene-β-D-fructopyranose-1′′-yl)-1′H-1′,2′, 3′-triazol-4′-yl}methyl]-5-fluorouracil) (E) and radiolabeled with 99mTc. It was analyzed by radio thin layer chromatography for quality control and stability. The radiolabeled complex was subjected to in vitro cell-binding studies to determine healthy and cancer cell affinity using HaCaT and MCF-7 cells, respectively. In addition, in vitro cytotoxicity studies of compound E were performed with HaCaT and MCF-5 cells. The radiochemical purity of the [99mTc]TcE was found to be higher than 90% at room temperature up to 6 hours. The radiolabeled complex showed higher specific binding to MCF-7 cells than HaCaT cells. IC50 values of E were found 31.5 ± 3.4 μM and 20.7 ± 2.77 μM for MCF-7 and HaCaT cells, respectively. The results demonstrated the potential of a new radiolabeled E with 99mTc has selective for breast cancer cells.
