- Direct Access to 2,3,4,6-Tetrasubstituted Tetrahydro-2H-pyrans via Tandem SN2′-Prins Cyclization
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A new, direct, and diastereoselective synthesis of activated 2,3,4,6-tetrasubstituted tetrahydro-2H-pyrans is described. In this reaction, iron(III) catalyzed an SN2′-Prins cyclization tandem process leading to the creation of three new stereoc
- Scoccia, Jimena,Pérez, Sixto J.,Sinka, Victoria,Cruz, Daniel A.,López-Soria, Juan M.,Fernández, Israel,Martín, Víctor S.,Miranda, Pedro O.,Padrón, Juan I.
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- Toward the construction of dermatan sulfate (DS) partial disaccharide library: Efficient synthesis of building blocks, common intermediate, and ligand conjugate of type-B DS disaccharide
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Dermatan sulfate (DS) is composed of a repeating disaccharide unit containing iduronic acid (IdoA) and N-acetylgalactosamine (GalNAc). In the divergent synthesis of DS disaccharide, it is important to prepare the IdoA moiety with a diverse set of protecti
- Kakitsubata, Yuhei,Aramaki, Rikiya,Nishioka, Kyosuke,Wakao, Masahiro,Suda, Yasuo
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- Properties, stability, assay, and preliminary pharmacokinetics of the immunomodulatory 1,2-O-isopropylidene-3-O-3'(N',N'-dimethylamino-n-propyl)-D-glucofuranose hydrochloride
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1,2-O-Isopropylidene-3-O-3(N',N'-dimethylamino-n-propyl)-D-glucufuranose hydrochloride (I) is a new agent with claimed immunomodulatory action and antiviral activity. Thin-layer chromatographic procedures and identifying tests were developed to separate the drug, its synthetic precursors, and solvolytic products, and were applied to stability studies. It is stable in 0.1N NaOH at 60° where its acid solvolysis product, 3-O-3'-(N',N'-dimethylamino-n-propyl)-D-glucose is readily degraded. The partition coefficient of I (pK'(a)=9.28) between chloroform and plasma was 6.4 ± 0.2 SEM between pH 10.5 and 11.0. Plasma and urine (0.5ml) adjusted to pH 11.0 were extracted with 10 ml of chloroform and the extract evaporated. The reconstituted residue in 50 μl of benzene, with the diiopropylaminoethyl analog of I as an internal standard, was derivatized with 50 μl of heptafluorobutyric anhydride at 60° for 45 min and was evaporated and reconstituted in 100 μl of benzene to be assayed for I by GLC with electron capture detection with a sensitivity of 5 ng/0.5 ml of biological fluid. The procedure was applied to pharmacokinetics in the dog and a two-compartment body model was observed with a terminal half-life of 103-130 min. At the 40mg dose, 60-40% was excreted renally unchanged and 20-34% as unidentified metabolites. At the 200-mg dose 82-85% was excreted renally unchanged and 15-17% as unidentified metabolites. The respective renal clerances of I were 135 and 163 ml/min. The respective total clearances of I were 204 and 191 ml/min. These metabolites were apparently unextracted with chloroform from biological fluids at pH 11 and the liquid scintillation counting (LSC) assay of extracted radiolabeled I appeared synonomous with the GLC assay of I in such fluids.
- Garrett,Van Peer,Mahrous,Schuermann
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- METHODS FOR MAKING DARUNAVIR P2-LIGAND PRECURSORS
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A method for making an optically active P2-ligand precursor comprising converting D-xylose or a derivative thereof or D-glucose or a derivative thereof to the optically active P2-ligand precursor.
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Paragraph 0008; 0022; 0033
(2022/02/28)
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- 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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- Visible-Light-Mediated Oxidative Debenzylation Enables the Use of Benzyl Ethers as Temporary Protecting Groups
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The cleavage of benzyl ethers by catalytic hydrogenolysis or Birch reduction suffers from poor functional group compatibility and limits their use as a protecting group. The visible-light-mediated debenzylation disclosed here renders benzyl ethers temporary protective groups, enabling new orthogonal protection strategies. Using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as a stoichiometric or catalytic photooxidant, benzyl ethers can be cleaved in the presence of azides, alkenes, and alkynes. The reaction time can be reduced from hours to minutes in continuous flow.
- Cavedon, Cristian,Sletten, Eric T.,Madani, Amiera,Niemeyer, Olaf,Seeberger, Peter H.,Pieber, Bartholom?us
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supporting information
p. 514 - 518
(2021/01/26)
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- Triethylamine-methanol mediated selective removal of oxophenylacetyl ester in saccharides
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A highly selective, mild, and efficient method for the cleavage of oxophenylacetyl ester protected saccharides was developed using triethylamine in methanol at room temperature. The reagent proved successful against different labile groups like acetal, ketal, and PMB and also generated good yields of the desired saccharides bearing lipid esters. Further, we also observed DBU in methanol as an alternative reagent for the deprotection of acetyl, benzoyl, and oxophenylacetyl ester groups. This journal is
- Rasool, Javeed Ur,Kumar, Atul,Ali, Asif,Ahmed, Qazi Naveed
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p. 338 - 347
(2021/01/29)
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- Method for synthesizing release type xylose ester perfume for tobacco perfuming
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A synthesis method of a release type xylose ester spice for flavoring tobacco is provided. The glucose is used as a raw material, the principle of esterifying carboxylic acid and alcohol to prepare ester is adopted, a common parent carboxylic acid which c
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Paragraph 0026-0028; 0041-0043; 0056-0058
(2021/10/27)
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- Me3SI-promoted chemoselective deacetylation: a general and mild protocol
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A Me3SI-mediated simple and efficient protocol for the chemoselective deprotection of acetyl groups has been developedviaemploying KMnO4as an additive. This chemoselective deacetylation is amenable to a wide range of substrates, tolerating diverse and sensitive functional groups in carbohydrates, amino acids, natural products, heterocycles, and general scaffolds. The protocol is attractive because it uses an environmentally benign reagent system to perform quantitative and clean transformations under ambient conditions.
- Gurawa, Aakanksha,Kashyap, Sudhir,Kumar, Manoj
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p. 19310 - 19315
(2021/06/03)
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- New Epoxy sugar based glucose derivatives as eco friendly corrosion inhibitors for the carbon steel in 1.0 M HCl: Experimental and theoretical investigations
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In this study, we chose to synthesize new sugar based glucose derivatives as ecological corrosion inhibitors for carbon steel in acidic medium. The products obtained in the form of syrupy liquids, and the purity of obtained compounds was characterized by NMR spectroscopy analysis. The corrosion inhibition activities for both compounds were evaluated by electrochemical and rheological methods. Thus, the results of the experimental tests have been confirmed by theoretical studies (DFT, MC and MD simulations). The surface study of carbon steel has been characterized by the scanning electron spectroscopy (SEM). The gravimetric solutions were identified using UV-Vis spectroscopy and Inductively Coupled Plasma-Optical Spectroscopy (ICP-OES).
- Berisha, A.,Dagdag, O.,Dohare, P.,Galai, M.,Lakhrissi, B.,Lakhrissi, L.,Rbaa, M.,Touhami, M. Ebn,Warad, I.,Zarrouk, A.
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- Near-infrared glucose fluorescence probe and preparation method thereof
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The invention relates to a near-infrared glucose fluorescent probe. The structural formula of the near-infrared glucose fluorescent probe is [Glu-1-O-DSCN (left), Glu-3-O-DSCN (middle), and Glu-2-N-DSCN (right)]. According to the near-infrared glucose fluorescent probe, an electron donor-acceptor structure (D-A) conjugated group DCSN is adopted as a fluorescent group, and the structural design ofthe DCSN-glucose probe is realized through an ether bond; the glucose group plays a specific recognition role in the probe, and water solubility and biocompatibility of a probe molecule can also be increased. According to the near-infrared glucose fluorescent probe, the raw materials are cheap and easy to obtain, the synthesis route is simple, and the glucose probe with strong penetrability, stable photochemistry, good biocompatibility, and high signal-to-noise ratio is obtained; and near-infrared glucose fluorescent probe can be applied to living cell staining, mitochondria localization, glucose tracking, brain tissue imaging, and tumor tissue labeling and identification.
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Paragraph 0052; 0096; 0103; 0104
(2020/01/14)
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- Synthesis and Structure-Activity Relationship Studies of C2-Modified Analogs of the Antimycobacterial Natural Product Pyridomycin
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A series of derivatives of the antimycobacterial natural product pyridomycin have been prepared with the C2 side chain attached to the macrocyclic core structure by a C-C single bond, in place of the synthetically more demanding enol ester double bond found in the natural product. Hydrophobic C2 substituents of sufficient size generally provide for potent anti-Mtb activity of these dihydropyridomycins (minimum inhibitory concentration (MIC) values around 2.5 μM), with several analogs thus approaching the activity of natural pyridomycin. Surprisingly, some of these compounds, in contrast to pyridomycin, are insensitive to overexpression of InhA in Mycobacterium tuberculosis (Mtb). This indicates that their anti-Mtb activity does not critically depend on the inhibition of InhA and that their overall mode of action may differ from that of the original natural product lead.
- Kienle, Maryline,Eisenring, Patrick,Stoessel, Barbara,Horlacher, Oliver P.,Hasler, Samuel,Van Colen, Gwéna?lle,Hartkoorn, Ruben C.,Vocat, Anthony,Cole, Stewart T.,Altmann, Karl-Heinz
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supporting information
p. 1105 - 1131
(2020/03/10)
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- Gram-level total synthesis method of sulfur onium salt type natural product neoponkoranol extracted from salacia plants
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The invention belongs to the field of chemical synthesis and particularly relates to a gram-level total synthesis method of a sulfur onium salt type natural product neoponkoranol with hypoglycemic activity extracted from salacia plants. According to the m
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Paragraph 0026; 0027; 00028
(2019/02/19)
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- GLUCOSIDE MONOMER, POLYMERIZATION COMPOSITION COMPRISING THE SAME AND HYDROGEL LENS USING THE SAME
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The present invention relates to a glucoside-based monomer represented by chemical formula 1, a polymeric composition for producing hydrogel comprising the same, and a hydrogel lens using the same. In the chemical formula 1, R_1 to R_4 is hydrogen, an alkyl group of C_1-C_4, or AA, R_6 is hydrogen or an alkyl group of C_1-C_4, at least one of the R_1 to R_4 is BB, R_5 is selected from hydrogen or CC, and m is an integer selected from 0 to 10. According to the present invention, hydrogel lenses having improved wettability can be provided.COPYRIGHT KIPO 2019
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Paragraph 0124-0130
(2019/08/22)
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- Total Synthesis and Anti-Cancer Activity of All Known Communesin Alkaloids and Related Derivatives
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A unified enantioselective total synthesis and anticancer evaluation of all known epoxide-containing communesin alkaloids and related derivatives is described. Our synthesis is predicated on the convergent and modular diazene-directed assembly of two comp
- Pompeo, Matthew M.,Cheah, Jaime H.,Movassaghi, Mohammad
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supporting information
p. 14411 - 14420
(2019/10/11)
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- Synthesis of (+)-altholactone, (+)-7-epi-altholactone, (?)-etharvensin, and (+)-alumheptolide-A using Pd-catalyzed carbonylation
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Syntheses of (+)-altholactone isolated from Goniothalamus giganteus and its C-7 epimer (+)-7-epi-altholactone, (?)-etharvensin and (+)-alumheptolide-A were achieved. The lactone ring of these compounds was constructed using Pd-catalyzed carbonylation.
- Miyazawa, Yuki,Hattori, Yasunao,Makabe, Hidefumi
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p. 4024 - 4027
(2018/10/05)
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- Novel Position-Specific 18O/16O Measurement of Carbohydrates. I. O-3 of Glucose and Confirmation of 18O/16O Heterogeneity at Natural Abundance Levels in Glucose from Starch in a C4 Plant
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The 18O/16O ratio at both molecular and positional levels in the carbohydrates of higher plants is a reliable proxy for the plant growth environment, and a potential indicator of the plant photosynthetic carbon assimilation mode, and its physiological, biochemical and metabolic status. The lack of exploitable nuclear resonance in 18O and 16O and the extremely low 17O abundance make the NMR-based PSIA (position-specific isotopic analysis) a significant challenge. In this Article, an alternative three-step wet chemistry based method for accessing the 18O/16O of glucose O-3 is presented. The O atoms (OH groups) at positions 1, 2, 5, and 6 were first protected by acetonation (converting glucose to 1,2;5,6-di-O-isopropylidene-glucofuranose). The protected glucose was then esterified at O-3 by thionoformylation. Subsequent Barton-McCombie deoxygenation quantitatively removed the O-3 from the protected sugar. Mass balance was then applied to calculate the 18O/16O of O-3 using the isotopic values of the protected sugar before and after the deoxygenation step. The method is innovative in that (i) isolation and purification of individual compounds for 18O by EA/Pyrolysis/IRMS analysis is unnecessary as the reaction mixture can be analyzed on a GC/Pyrolysis/IRMS; (ii) sample quantity is dramatically reduced; and (iii) the approach to access the O-3 isotopic signal can be easily expanded to other positions within glucose and other sugars. It was shown that O-3 is enriched by 12 mUr relative to the molecular average (O-2-O-6) for a glucose of C4 photosynthetic origin. We highlighted the potential applications of the intramolecular O isotopic heterogeneity of glucose this method revealed.
- Ma, Ran,Zhu, Zhenyu,Wang, Bo,Zhao, Yu,Yin, Xijie,Lu, Fengyan,Wang, Ying,Su, Jing,Hocart, Charles H.,Zhou, Youping
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p. 10293 - 10301
(2018/09/06)
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- Sulfonic Acid Functionalized Ordered Mesoporous Silica and their Application as Highly Efficient and Selective Heterogeneous Catalysts in the Formation of 1,2-Monoacetone-D-glucose
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A series of sulfonic acid functionalized ordered mesoporous silica (OMS), designated as RSO3H-OMS (R=alkyl or aryl; OMS=MCM-41, IITM-56 or SBA-15), were prepared by post-synthesis grafting method. These catalysts, in general, exhibit strong acidic sites and, therefore, yield diacetone-D-glucose as main product in the D-glucose acetonation reaction. On the other hand, the functionalized catalyst can also be tuned in such a way to generate significant amount of weak-to-moderate acidic sites, which are in turn responsible for the formation of 1,2-monoacetone-D-glucose, hitherto not reported so far. These functionalized materials also show promise as they are water tolerant catalyst as well as exhibit varying acidic strengths, which allow greater flexibility for the desired product. In addition, the uniform mesopores with high surface area permit bulkier molecules to enter the active sites, thus the catalyst offers larger pliability in terms of yield and reusability. We report here, for the first time, RSO3H-SBA-15, with sizable amount of weak-to-moderate acidic sites, as a robust heterogeneous catalyst for the formation of the targeted molecule, 1,2-monoacetone-D-glucose.
- Krishna, Nunna V.,Anuradha, Sankaran,Ganesh, Reddi,Kumar, Velisoju V.,Selvam, Parasuraman
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p. 5610 - 5618
(2018/11/27)
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- FUCOSIDASE INHIBITORS
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The present disclosure relates, in general, to compounds useful as inhibitors of fucosidase enzymes, and to methods and compositions for the treatment of tumors or cancers, such as liver disorders and liver tumors (e.g., hepatocellular carcinoma), with a compound as disclosed herein.
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Page/Page column 24
(2017/02/24)
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- Larger laboratory scale synthesis of 5-methyluridine and formal synthesis of its L-enantiomer
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A larger laboratory scale synthesis (>60 g per run) of 5-methyluridine is presented. The critical intermediate 1,2-O-isopropylidene-α-D-ribofuranose was prepared from very cheap D-glucose via D-allose. Its L-enantiomer was obtained from L-arabinose via L-glucose, and also from L-xylose. {figure presented}.
- Thiesen, Luciano J. Hoeltgebaum,Cabral, Nadia,Joselice E Silva, Maria,Bezerra, Gilson,Doboszewski, Bogdan
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p. 249 - 264
(2017/06/19)
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- Total syntheses of Prelactone V and Prelactone B
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The total syntheses of natural products Prelactone-V and Prelactone-B have been accomplished by a novel Chiron approach starting from D-glucose. The synthesis involves isopropylidene acetal formation of D-glucose using Poly(4-vinylpyridine) supported iodine as a catalyst, Tebbe olefination, Grignard reaction, Wittig olefination, selective mono deprotection of acetal using PMA/SiO2, hydrogenation and anti-1,3-diol formation are as key steps.
- Raghavendra,Tadiparthi, Krishnaji,Yadav
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supporting information
p. 17 - 19
(2017/03/15)
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- An eco-compatible strategy for the diversity-oriented synthesis of macrocycles exploiting carbohydrate-derived building blocks
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An efficient, eco-compatible diversity-oriented synthesis (DOS) approach for the generation of library of sugar embedded macrocyclic compounds with various ring size containing 1,2,3-triazole has been developed. This concise strategy involves the iterative use of readily available sugar-derived alkyne/azide-alkene building blocks coupled through copper catalyzed azide-alkyne cycloaddition (CuAAC) reaction followed by pairing of the linear cyclo-adduct using greener reaction conditions. The eco-compatibility, mild reaction conditions, greener solvents, easy purification and avoidance of hazards and toxic solvents are advantages of this protocol to access this important structural class. The diversity of the macrocycles synthesized (in total we have synthesized 13 macrocycles) using a set of standard reaction protocols demonstrate the potential of the new eco-compatible approach for the macrocyclic library generation.
- Maurya, Sushil K.,Rana, Rohit
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supporting information
p. 1106 - 1118
(2017/06/21)
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- Synthesis and glycosidase inhibition evaluation of (3S,4S)-3-((R)-1,2-dihydroxyethyl)pyrrolidine-3,4-diol
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A new azasugar (3S,4S)-3-((R)-1,2-dihydroxyethyl)pyrrolidine-3,4-diol (1) was obtained from commercially available D-glucose using one-pot reductive cyclization as a key step. The target product, i.e., the iminosugar isomer, was obtained in 10 steps and 24.3% overall yield. Only three column chromatography purifications were needed in this synthesis. The biological activity of the target molecule as glycosidase inhibitor was studied, but the inhibitory activity against four glycosidases was not good (IC50?>?100?μM).
- Zhang, En,Bai, Peng-Yan,Sun, Wei,Wang, Shang,Wang, Ming-Ming,Xu, Shuai-Min,Liu, Hong-Min
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- Synthesis and Evaluation of 2′-Deoxy-2′-Spirodiflurocyclopropyl Nucleoside Analogs
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The preparation of 2′-deoxy-2′-siprodifluorocyclopropany-lnucleoside analogs has been achieved from α-d-glucose in several steps. The key step in the synthesis was the introduction of the difluorocyclopropane through a difluorocarbene type reaction at the 2′-position. Then, a series of novel 2′-deoxy-2′-spirodifluorocyclopropanyl nucleoside analogs were synthesized using the Vorbrüggen method. All the synthesized nucleosides were characterized and subsequently evaluated against hepatitis C and influenza A virus strains in vitro.
- Liu, Xiao,Xia, Xueliang,Sun, Chenghai,Lin, Cai,Zhou, Yiqian,Hussain, Muzammal,Tang, Fei,Liu, Lu,Li, Xue,Zhang, Jiancun
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p. 479 - 494
(2016/09/04)
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- Structurally Simple Benzyl-Type Photolabile Protecting Groups for Direct Release of Alcohols and Carboxylic Acids
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Structurally simple benzyl-type photolabile protecting groups (PPGs) have been developed to release alcohols and carboxylic acids. Release of two substrates from one PPG chromophore has also been accomplished. (Chemical Equation Presented).
- Wang, Pengfei,Lu, Wenya,Devalankar, Dattatray A.,Ding, Zhenying
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supporting information
p. 2114 - 2117
(2015/05/13)
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- Synthesis and in vitro bioactivity evaluation of new glucose and xylitol ester derivatives of 5-aminosalicylic acid
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New glucose and xylitol esters of 5-amino salicylic acid (5-ASA) were synthesized followed by evaluation of their in vitro antimicrobial, anti-cancer and anti-inflammatory activities. The results of the antimicrobial activity assessment revealed that the new final esters were more effective against Gram-negative as well as Gram-positive bacteria than the original drug. Furthermore, the new final products were confirmed by a cytotoxicity assay over HT-29 and 3T3 cell lines to be less toxic for normal cells compared to the initial drug. On the other hand, however, their suppressive effect against cancerous cells was somewhat lower. Meanwhile, the anti-inflammatory activity assay over a RAW264.7 macrophage cell line demonstrated that the NO inhibition activity of the conjugated drug to the previously mentioned saccharides, especially to glucose, has slightly improved compared to the non-conjugated drug. Finally, in silico screening was also performed in order to predict the potential interactions and binding energy of the novel products against cyclooxygenase (COX-1/COX-2) and lipoxygenase (5-LOX) proteins. Findings indicated that the new products had greater hydrogen bonds and binding affinities with the active sites of proteins towards 5-ASA.
- Yousefi, Samira,Bayat, Saadi,Abdul Rahman, Mohd Basyaruddin,Ismail, Intan Safinar,Saki, Elnaz,Abdulmalek, Emilia
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p. 97295 - 97307
(2015/11/28)
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- Titanocene dihalides and ferrocenes bearing a pendant α-d- xylofuranos-5-yl or α-d-ribofuranos-5-yl moiety. synthesis, characterization, and cytotoxic activity
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Titanocene dichlorides of general formula [(η5-C 5H5)(η5-C5H4R) TiCl2] (where R = 5-deoxy-1,2-di-O-isopropylidene-3-O-benzyl-α- d-xylofuranos-5-yl (Xylf) (8a); R = 5-deoxy-1,2-di-O-isopropylidene-3-O-benzyl- α-d-ribofuranos-5-yl (Ribf) (8b)) and [(η5-C 5H4R)2TiCl2] (R = Xylf (9a); R = Ribf (9b)) were prepared by reaction of the corresponding lithium cyclopentadienides 7a,b with an equimolar amount of [(η5-C 5H5)TiCl3] or a 0.5 mol amount of [TiCl 4(THF)2]. Titanocene difluorides of the general formula [(η5-C5H4R1)(η5- C5H4R2)TiF2] (R1 = H and R2 = Ribf (10); R1 = R2 = Xylf (11a); R 1 = R2 = Ribf (11b)) were obtained by fluorination of the corresponding titanocene dichlorides 8b and 9 with the fluorinating agent {2-(CH2NMe2)C6H4-κC,N}(n-Bu) 2SnF in high yields. Alternatively, complexes 11 were prepared in a straightforward way by direct reaction of [TiF4(THF)2] with 2 equiv of the corresponding lithium cyclopentadienide 7a,b. Ferrocene complexes [(η5-C5H4R)2Fe] (R = Xylf (12a); R = Ribf (12b)) were synthesized by metathesis of 2 equiv of lithium cyclopentadienide 7a,b and 1 equiv of anhydrous FeCl2. Deprotection of the benzyl group in ferrocenes 12 proceeded cleanly by a catalytic hydrogenation on Pd/C and afforded the ferrocene diols [(η5- C5H4R)2Fe] (R = 5-deoxy-1,2-di-O- isopropylidene-α-d-xylofuranos-5-yl (Xylf-OH) (14a); R = 5-deoxy-1,2-di-O-isopropylidene-α-d-ribofuranos-5-yl (Ribf-OH) (14b)). A scaled up benzyl deprotection with Et3SiH as a hydrogen source led to the replacement of only one benzyl group, which gave the ferrocene alcohol [(η5-C5H4R1)(η5- C5H4R2)Fe] (R1 = Xylf and R 2 = Xylf-OH (13)). The prepared complexes were characterized by elemental analysis, melting point determination, NMR, IR, and ESI-MS, and the molecular structure of 9b was determined by X-ray diffraction analysis. The cytotoxic activity of complexes 8-14 against A2780 and A2780cis cancer cells was evaluated by MTT tests. Titanocene difluorides 10 and 11 and ferrocene diol 14a showed cytotoxicity against A2780 cells in the medium to low micromolar range, while the most active species, 11b, displayed about 40% higher cytotoxicity against A2780cis in comparison to a cisplatin standard.
- Hodik, Tomas,Lamac, Martin,Cervenkova St'Astna, Lucie,Karban, Jindrich,Koubkova, Lucie,Hrstka, Roman,Cisarova, Ivana,Pinkas, Jiri
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p. 2059 - 2070
(2014/05/20)
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- Synthesis and oxidation of thioglicosides underlain by neomenthanethiol, D-glucose, and D-fructose
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Synthesis of sulfides proceeding from neomenthanethiol, 1,2-O-isopropylidene-α-D-glucofuranose and 2,3:4,5-di-O-isopropylidene- β-D-fructopyranose was performed to get 65 and 54% yield respectively. Oxidation of the sulfides afforded diastereomeric sulfoxides in the yields from 40 to 53%, and diastereomeric excess (de) up to 36%. After removing the isopropylidene protection from 1-deoxy-1-[(1S,2S,5R)-2-isopropyl-5- methylcyclohexylsulfanyl]-2,3:4,5-di-O-isopropylidene-β-D-fructopyranose a water-soluble sulfide was obtained.
- Pestova,Izmest'Ev,Rubtsova,Kuchin
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p. 670 - 677
(2014/07/08)
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- Glucose positions affect the phloem mobility of glucose-fipronil conjugates
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In our previous work, a glucose-fipronil (GTF) conjugate at the C-1 position was synthesized via click chemistry and a glucose moiety converted a non-phloem-mobile insecticide fipronil into a moderately phloem-mobile insecticide. In the present paper, fipronil was introduced into the C-2, C-3, C-4, and C-6 positions of glucose via click chemistry to obtain four new conjugates and to evaluate the effects of the different glucose isomers on phloem mobility. The phloem mobility of the four new synthetic conjugates and GTF was tested using the Ricinus seedling system. The results confirmed that conjugation of glucose at different positions has a significant influence on the phloem mobility of GTF conjugates.
- Lei, Zhiwei,Wang, Jie,Mao, Genlin,Wen, Yingjie,Tian, Yuxin,Wu, Huawei,Li, Yufeng,Xu, Hanhong
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p. 6065 - 6071
(2015/04/22)
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- Regioselective oxidative cleavage of benzylidene acetals of glycopyranosides with periodic acid catalyzed by tetrabutylammonium bromide
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A combination of periodic acid, tetrabutylammonium bromide, and wet alumina in dichloromethane efficiently oxidized benzylidene acetals of carbohydrates to the corresponding hydroxybenzoates in excellent yields (>90%). Under these conditions, other protec
- Vatèle, Jean-Michel
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supporting information
p. 115 - 119
(2014/01/06)
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- Synthesis and NMR elucidation of four novel 2-(trimethylsilyl)ethyl glycosides
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Four novel 2-(trimethylsilyl)ethyl glycosides have been synthesized by a short and efficient route starting from d-glucose. Their structures were elucidated by applying high-resolution mass spectra, and one-dimensional and two-dimensional NMR techniques.
- Qu, Huanhuan,Sun, Wenji,Zhang, Yanyan,Sollogoub, Matthieu,Zhang, Yongmin
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p. 1557 - 1564
(2014/05/06)
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- Glucose positions affect the phloem mobility of glucose-fipronil conjugates
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In our previous work, a glucose-fipronil (GTF) conjugate at the C-1 position was synthesized via click chemistry and a glucose moiety converted a non-phloem-mobile insecticide fipronil into a moderately phloem-mobile insecticide. In the present paper, fipronil was introduced into the C-2, C-3, C-4, and C-6 positions of glucose via click chemistry to obtain four new conjugates and to evaluate the effects of the different glucose isomers on phloem mobility. The phloem mobility of the four new synthetic conjugates and GTF was tested using the Ricinus seedling system. The results confirmed that conjugation of glucose at different positions has a significant influence on the phloem mobility of GTF conjugates.
- Lei, Zhiwei,Wang, Jie,Mao, Genlin,Wen, Yingjie,Tian, Yuxin,Wu, Huawei,Li, Yufeng,Xu, Hanhong
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p. 6065 - 6071
(2014/07/21)
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- Synthesis of glucose-tagged triazolium ionic liquids and their application as solvent and ligand for copper(I) catalyzed amination
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Glucose-linked 1,2,3-triazolium ionic liquids have been synthesized as a new class of chiral solvents by copper(I) catalyzed regioselective cycloaddition of a glucose azide with a glucose alkyne followed by quaternization with methyl iodide. The tagging of glucose to triazolium core makes these molecules act as reusable ligand and solvent in copper(I) catalyzed amination of aryl halides with aqueous ammonia. While the free hydroxyl groups of sugar help in stabilizing copper(I) species during the reaction thus acting as a ligand, the triazolium salt which makes it a liquid at room temperature serves as a reusable solvent. These chiral ionic liquids derived from low-cost natural sources can find utility in various transition-metal catalyzed reactions, and can be explored for asymmetric synthesis in future.
- Jha, Abadh Kishor,Jain, Nidhi
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supporting information
p. 4738 - 4741
(2013/08/23)
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- Lewis acid-assisted olefin cross-metathesis reaction: An efficient approach for the synthesis of glycosidic-pyrroloquinolinone based novel building blocks of camptothecin and evaluation of their antitumor activity
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A series of glycosidic-pyrroloquinolinone based novel building blocks of camptothecin (2a-g) were synthesized via Lewis acid-assisted olefin cross-metathesis reaction using Ti(OiPr)4 30 mol % and 10 mol % of Grubb's second generation catalyst with good to excellent yields. Most of these compounds exhibited significant growth inhibitory effects on all the tested cancer cell lines and three compounds (2c, 2d and 2e) showed potent cytotoxic activity.
- Nagarapu, Lingaiah,Gaikwad, Hanmant K.,Bantu, Rajashaker,Ganesh Kumar,Pombala, Sujitha
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supporting information; scheme or table
p. 1287 - 1291
(2012/03/27)
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- Hybrids of privileged structures benzothiazoles and pyrrolo[2,1-c] [1,4]benzodiazepin-5-one, and diversity-oriented synthesis of benzothiazoles
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Privileged structures like Benzothiazole and Pyrrolobenzodiazepine offer wonderful opportunity to explore in anti-cancer drug discovery as a mean to counter drug-resistance problem. BT-PBD hybrids and diverse BT derivatives have been synthesized and their in vitro cytotoxic activities were screened against five cancer cell lines have been discussed. The novel compounds showed promising results as compared with the marketed drug etoposide and could well be used in future anti-cancer drug development studies.
- Subhas Bose,Idrees, Mohd.,Todewale, Ismail K.,Jakka,Venkateswara Rao
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body text
p. 27 - 38
(2012/07/01)
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- Non-symmetric liquid crystal dimer containing a carbohydrate-based moiety
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The synthesis and characterisation of a novel non-symmetric liquid crystal dimer, 1-[3-O-(d-glucopyranos-3-yl)]-8-[(4-methoxyazobenzene-4′-oxy)] octane is reported. This exhibits glassy behaviour and a highly interdigitated smectic A phase in which the aromatic and alkyl structural fragments overlap. Variable temperature infrared spectroscopy reveals that the strength and extent of hydrogen bonding within the system does not show a marked change at either the glass transition or at the smectic A-isotropic transition. This observation indicates that the smectic A-isotropic transition is driven by changes in the van der Waals interactions between the molecules while hydrogen bonded aggregates persist into the isotropic phase.
- Cook, Andrew G.,Wardell, James L.,Brooks, Nicholas J.,Seddon, John M.,Martinez-Felipe, Alfonso,Imrie, Corrie T.
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- Sugar-amino acid cyclic conjugates as novel conformationally constrained hydroxyethylamine transition-state isosteres
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Hydroxyethylamine (HEA) isosteres have previously been shown to display a multitude of biomedical applications. In fact, the first protease inhibitor, saquinavir is an HEA based peptidomimetic. Herein we describe an easy-to-operate synthetic route to a series of carbohydrate-based conformationally constrained hydroxyethylamine (HEA) isosteres featuring amino acid side chains, starting from d-glucose. This class of novel sugar-amino acid-tethered conformationally restricted HEA systems may have bearing in practical application, particularly in the development of conformationally restricted protease inhibitors.
- Roy, Arup,Sanjayan, Gangadhar J.
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supporting information; scheme or table
p. 3361 - 3363
(2012/07/28)
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- Synthesis of 1,2,3-triazole glycoconjugates as inhibitors of α-glucosidases
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Ten new 1,2,3-triazole glycoconjugates were synthesized from d-glucose and evaluated in in vitro assays for their ability to inhibit the enzyme α-glucosidase. Most of the compounds had low activity or were inactive when compared with acarbose. However, the derivative 1,2-O-isopropylidene-3- phenyl-5-(4-phenyl-1H-1,2,3-triazole-1-yl)-α-d-ribofuranose (19i) possessed activity comparable with the standard drug. The influence of the phenyl group on carbon 3 of the carbohydrate framework is discussed.
- Da Rocha, David R.,Santos, Wilson C.,Lima, Emerson S.,Ferreira, Vitor F.
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scheme or table
p. 14 - 19
(2012/03/26)
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- Synthesis from d-altrose of (5 R,6 R,7 R,8 S)-5,7-dihydroxy-8- hydroxymethylconidine and 2,4-dideoxy-2,4-imino-d-glucitol, azetidine analogues of swainsonine and 1,4-dideoxy-1,4-imino-d-mannitol
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Ring closure of a 3,5-di-O-triflate derived from d-altrose with benzylamine allowed the formation of both monocyclic and bicyclic azetidine analogues of swainsonine.
- Araújo, Noelia,Jenkinson, Sarah F.,Martínez, R. Fernando,Glawar, Andreas F. G.,Wormald, Mark R.,Butters, Terry D.,Nakagawa, Shinpei,Adachi, Isao,Kato, Atsushi,Yoshihara, Akihide,Akimitsu, Kazuya,Izumori, Ken,Fleet, George W. J.
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supporting information; experimental part
p. 4174 - 4177
(2012/10/23)
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- Synthesis of a MUC1-glycopeptide-BSA conjugate vaccine bearing the 3′-deoxy-3′-fluoro-Thomsen-Friedenreich antigen
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A novel MUC1-glycopeptide-BSA conjugate vaccine with a specifically fluorinated Thomsen-Friedenreich antigen side chain at Thr6 was prepared. Preliminary immunological experiments reveal specific binding of the tumor-associated glycopeptide antigen analog by anti-MUC1-mouse antibodies.
- Hoffmann-Roeder, Anja,Johannes, Manuel
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supporting information; experimental part
p. 9903 - 9905
(2011/10/09)
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- Organoiridium complexes: Efficient catalysts for the formation of sugar acetals and ketals
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[Cp*IrCl2]2 is used as an efficient promoter for the synthesis of sugar acetals and ketals with good to excellent yields. The catalyst is found to be general for a wide range of sugars.
- Mandal, Soumik,Verma, Prashant Ranjan,Mukhopadhyay, Balaram,Gupta, Parna
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experimental part
p. 2007 - 2010
(2011/12/01)
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- Sugar-monophosphite ligands applied to the asymmetric Ni-catalyzed trialkylaluminum addition to aldehydes
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A series of readily available sugar-based phosphite ligands were applied to the Ni-catalyzed asymmetric trialkylaluminum additions to aldehydes. The ability of the catalysts to transfer chiral information to the product could be tuned by choosing suitable ligand components (configuration at C-3 of the furanoside backbone; the steric hindrance of the substituent at C-3 and the substituents/configuration of the biaryl phosphite moieties). Good enantioselectivities (ee's up to 84%) were obtained for several aryl aldehydes using several organoaluminum sources.
- Alegre, Sabina,Dieguez, Montserrat,Pmies, Oscar
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scheme or table
p. 834 - 839
(2011/08/22)
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- Tetrabutylammonium tribromide (TBATB): A mild and efficient catalyst for O-isopropylidenation of carbohydrates
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A wide range of O-isopropylidene derivatives can be prepared from the sugars and their derivatives on reaction with acetone at room temperature by employing 2 mol % of tetrabutylammonium tribromide (TBATB) as a catalyst. Good yields, low catalyst loading, mild reaction conditions, and a non-aqueous workup procedure are some major advantages of this protocol.
- Khan, Abu T.,Khan, Md. Musawwer,Adhikary, Anubendu
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experimental part
p. 673 - 677
(2011/04/26)
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- Synthesis and biological evaluation of sugar-derived chiral nitroimidazoles as potential antimycobacterial agents
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Chiral nitroimidazoles were synthesized using sugars as the chiral source. The synthesized compounds showed promising antimycobacterial property with MIC value in the range 6.25-12.5 μg/mL against Mycobacterium tuberculosis H 37Rv.
- Mugunthan,Sriram, Dharmarajan,Yogeeswari, Perumal,Kartha, K. P. Ravindranathan
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scheme or table
p. 1760 - 1766
(2011/12/01)
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- A simple and convenient synthetic protocol for O-isopropylidenation of sugars using bromodimethylsulfonium bromide (BDMS) as a catalyst
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Various O-isopropylidene derivatives of sugars and acyclic sugars were obtained in very good yields on reaction with acetone at room temperature with a catalytic amount of bromodimethylsulfonium bromide (BDMS). These O-isopropylidene derivatives can also be prepared in good yields on reaction with 2,2-dimethoxypropane (DMP) in acetonitrile using the same catalyst in shorter reaction times. Some of the advantages of this method are high effectiveness, a nonaqueous workup procedure, economic viability, and good yields.
- Khan, Abu T.,Musawwer Khan
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experimental part
p. 154 - 159
(2011/03/19)
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- Synthesis, Biological Activity, and Molecular Modeling Studies of 1H-1,2,3-Triazole Derivatives of Carbohydrates as a-Glucosidases Inhibitors
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A class of drugs in use for treating type II diabetes mellitus (T2D), typified by the pseudotetrasaccharide acarbose, act by inhibiting the a-glucosidase activity present in pancreatic secretions and in the brush border of the small intestine. Herein, we report the synthesis of a series of 4-substituted 1,2,3-triazoles conjugated with sugars, including D-xylose, D-galactose, D-allose, and D-ribose. Compounds were screened for a-glucosidase inhibitory activity using yeast maltase (MAL12) as a model enzyme. Methyl2,3-O-isopropylidene-β-D-ribofuranosides, such as the 4-(l-cyclohexenyl)-l,2,3-triazole derivative, were among the most active compounds, showing up to 25-fold higher inhibitory potency than the complex oligosaccharide acarbose. Docking studies on a MAL12 homology model disclosed a binding mode consistent with a transition-state-mimicking mechanism. Finally, the actual pharmacological potential of this triazole series was demonstrated by the reduction of postprandial blood glucose levels in normal rats. These compounds could represent new chemical scaffolds for developing novel drugs against T2D.
- Ferreira, Sabrinab,Sodero, Ana C. R.,Cardoso, Mariana F. C.,Lima, Emerson S.,Kaiser, Carlos R.,Silva Jr., Floriano P.,Ferreira, Vitor F.
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supporting information; experimental part
p. 2364 - 2375
(2010/09/04)
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- Diastereoselective synthesis of tetrahydrofurans from Aryl 3-chloropropylsulfoxides and aldehydes
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Carbanions of aryl 3-chloropropylsulfoxides react with nonenolizable aldehydes to give 2,3-disubstituted tetrahydrofurans. Deprotonation of the sulfoxides carried out in the presence of aldehydes results in the addition of the carbanions to the carbonyl group of the aldehydes, followed by 1,5-intramolecular substitution of the resulting aldol-type anion to produce the tetrahydrofuran ring. The 2-aryl and 3-arylsulfinyl substituents are always in trans relation, and the reaction proceeds with high diastereoselectivity also in respect to the chiral sulfur atom. The diastereoselectivity is attributed to the cyclic transition state of the aldol addition and increases when the aromatic ring of the sulfoxide contains electron-withdrawing substituents, whereas that of the aldehyde has electron-donating groups.
- Komsta, Zofia,Barbasiewicz, Michal,Makosza, Mieczyslaw
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supporting information; experimental part
p. 3251 - 3259
(2010/08/19)
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- (2-Nitrophenyl)acetyl: A new, selectively removable hydroxyl protecting group
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Figure presented The utility of the (2-nitrophenyl)acetyl (NPAc) group for the protection of hydroxyl functions is reported. (2-Nitrophenyl)acetates are readily prepared starting from the commercially available, inexpensive (2-nitrophenyl)acetic acid, and these esters are stable under a series of common carbohydrate transformations. The NPAc group can be removed selectively using Zn and NH4Cl without affecting a series of common protecting groups. This new protecting group is orthogonal with the commonly used tert-butyldimethylsilyl, levulinoyl, 9-fluorenylmethoxycarbonyl, naphthylmethyl, and p-methoxybenzyl groups.
- Daragics, Katalin,Fuegedi, Peter
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supporting information; experimental part
p. 2076 - 2079
(2010/09/15)
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- Synthesis and antibacterial activity of aminodeoxyglucose derivatives against Listeria innocua and Salmonella typhimurium
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In this study aminodeoxyglucose derivatives were synthesized and evaluated for their antibacterial activity against two food bacteria, Listeria innocua and Salmonella typhimurium. 6-Amino-6-deoxy-α-Dmethylglucopyranose (GSA-6), 3-amino-3-deoxy-D-glucopyranoside (GSA-3), and β-D-glucopyranosylamine (GSA-1) were synthesized and concurrently tested with commercially available D-glucosamine (GSA-2) for antibacterial activity. Results obtained from this study showed a pronounced antagonist effect due to the position of amino groups of aminoglucose derivatives on the antibacterial activity. GSA-3 was the most active compound. At a concentration of 2 × 10 -4 mol mL -1, it delayed the growth of both bacteria with percentages of inhibition of 29 and 15% for L. innocua and S. typhimurium, respectively. At the same concentration the percentages of inhibition for other aminodeoxyglucoses varied between 5 and 18% and between 2 and 11% for L. innocua and S. typhimurium, respectively. All compounds were characterized by FTIR, 1H NMR, and 13C NMR spectroscopy.
- Theoneste, Muhizi,Stephane, Greller,Veronique, Coma
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experimental part
p. 8770 - 8775
(2010/07/17)
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- Large scale synthesis of the acetonides of l-glucuronolactone and of l-glucose: easy access to l-sugar chirons
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1,2-O-Isopropylidene-α-l-glucurono-3,6-lactone may be synthesized on a 100-200 g scale from cheaply available d-glucoheptonolactone in an overall yield of 94% in four steps via l-glucuronolactone. Subsequent elaboration to l-glucose, diacetone-l-glucose (1,2:5,6-di-O-isopropylidene-α-l-glucofuranose), and monoacetone-l-glucose (1,2-O-isopropylidene-α-l-glucofuranose) allows easy access to a range of l-sugar chirons.
- Weymouth-Wilson, Alexander C.,Clarkson, Robert A.,Jones, Nigel A.,Best, Daniel,Wilson, Francis X.,Pino-González, Maria-Soledad,Fleet, George W.J.
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experimental part
p. 6307 - 6310
(2010/01/18)
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