- Synthesis of Glycosyl Fluorides by Photochemical Fluorination with Sulfur(VI) Hexafluoride
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This study describes a new convenient method for the photocatalytic generation of glycosyl fluorides using sulfur(VI) hexafluoride as an inexpensive and safe fluorinating agent and 4,4′-dimethoxybenzophenone as a readily available organic photocatalyst. This mild method was employed to generate 16 different glycosyl fluorides, including the substrates with acid and base labile functionalities, in yields of 43%-97%, and it was applied in continuous flow to accomplish fluorination on an 7.7 g scale and 93% yield.
- Bannykh, Anton,Khomutnyk, Yaroslav,Kim, Sungjin,Nagorny, Pavel
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p. 190 - 194
(2021/01/13)
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- TRITERPENE SAPONIN SYNTHESIS, INTERMEDIATES AND ADJUVANT COMBINATIONS
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The present application relates to triterpene glycoside saponin-derived adjuvants, syntheses thereof, and intermediates thereto. The application also provides pharmaceutical compositions comprising compounds of the present invention and methods of using said compounds or compositions in the treatment of and immunization for infectious diseases.
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- Ring-opened 4-hydroxy-δ-valerolactone subunit as a key structural fragment of polyesters that degrade without acid formation
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Random copolymers of ?-caprolactone with O-benzyl-protected 4-hydroxy- or 2,4-dihydroxy-δ-valerolactone after hydrogenation form γ-hydroxy functionalized polyesters that degrade via the cyclization to γ-butyrolactone fragments without carboxylic acid formation.
- Nifant'ev, Ilya E.,Shlyakhtin, Andrey V.,Bagrov, Vladimir V.,Ezhov, Roman N.,Lozhkin, Boris A.,Churakov, Andrei V.,Ivchenko, Pavel V.
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p. 629 - 631
(2018/12/13)
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- Intramolecular Tandem Seleno-Michael/Aldol Reaction: A Simple Route to Hydroxy Cyclo-1-ene-1-carboxylate Esters
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Intramolecular tandem seleno-Michael/aldol reaction followed by an oxidation-elimination process can be an efficient tool for the construction of hydroxy cyclo-1-ene-1-carboxylate esters from oxo-α,β-unsaturated esters. Generation of lithium selenolate from elemental selenium and n-BuLi provides a simple and efficient one-pot access to cyclic endo-Morita-Baylis-Hillman adducts.
- Banachowicz, Piotr,Mlynarski, Jacek,Buda, Szymon
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p. 11269 - 11277
(2018/09/06)
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- Synthesis of Phenolic Glycosides: Glycosylation of Sugar Lactols with Aryl Bromides via Dual Photoredox/Ni Catalysis
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Multifarious sugar lactols were efficiently transformed into the corresponding phenolic glycosides by treating with aryl bromides in acetonitrile with Ir[dF(CF3)ppy]2(dtbbpy)(PF6) as a photocatalyst under visible light irr
- Ye, Hui,Xiao, Cong,Zhou, Quan-Quan,Wang, Peng George,Xiao, Wen-Jing
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supporting information
p. 13325 - 13334
(2018/11/02)
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- A Kinsenoside and GoodyerosideA analogs of the preparation and use thereof
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The invention discloses a preparation method and application of compounds as shown in formula I and II, and in particular relates to preparation of Kinsenoside or GoodyerosideA analogue and medical application of the Kinsenoside or GoodyerosideA analogue
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Paragraph 0050; 0051; 0052; 0053; 0054
(2017/06/14)
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- Automated glycan assembly of xyloglucan oligosaccharides
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We report the automated glycan assembly of oligosaccharide fragments related to the hemicellulose xyloglucan (XG). Iterative addition of monosaccharide and disaccharide building blocks to a solid support provided seven cellulose and xyloglucan fragments i
- Dallabernardina, Pietro,Schuhmacher, Frank,Seeberger, Peter H.,Pfrengle, Fabian
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supporting information
p. 309 - 313
(2015/12/30)
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- Glucosylceramide mimics: Highly potent GCase inhibitors and selective pharmacological chaperones for mutations associated with types 1 and 2 gaucher disease
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A series of iminoxylitol derivatives carrying a C-linked di-O-acyl or di-O-alkyl glyceryl substituent were prepared and characterized. All of these compounds, which were designed as glucosylceramide (GlcCer) mimics, were nanomolar inhibitors of lysosomal b-glucosidase (glucocerebrosidase, GCase). Two of these pseudoglycolipids were further evaluated for their ability to enhance the activity of mutant GCase in human Gaucher cells. Although the di-O-hexyl ether was surprisingly devoid of chaperoning activity on both N370S and L444P GCases, the di-Odecanoyl ester was a potent chaperone of the L444P hydrolase, capable of increasing the residual activity of the enzyme by a factor of two at a very low concentration (50 nm); such a significant effect on the L444P mutation in human fibroblasts has not yet been observed. In heat-stress studies, the diether was found to be much more effective in stabilizing the wildtype enzyme than the diester. Four representative pseudoglycolipids were also assayed as inhibitors of GlcCer synthase, because such compounds could find use in the substrate reduction therapy approach to treat lysosomal storage diseases, but these compounds revealed only moderate activity. As efficient pharmacological chaperones, new structures such as the di-C10-ester constitute leads for the development of therapeutic agents for types 2 and 3 Gaucher disease, the most severe neuronopathic forms of this lysosomal disease.
- Schcnemann, Wojciech,Gallienne, Estelle,Ikeda-Obatake, Kyoko,Asano, Naoki,Nakagawa, Shinpei,Kato, Atsushi,Adachi, Isao,Górecki, Marcin,Frelek, Jadwiga,Martin, Olivier R.
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p. 1805 - 1817
(2014/01/06)
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- An improved methodology for the synthesis of 1-C-allyl imino-d-xylitol and -l-arabinitol and their rapid functionalization
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As part of our research program dedicated to the design and synthesis of new iminosugars as pharmacological chaperones for the treatment of lysosomal storage disorders, we developed a rapid and efficient methodology for the access to functionalized and no
- Biela, Anna,Oula?di, Farah,Gallienne, Estelle,Górecki, Marcin,Frelek, Jadwiga,Martin, Olivier R.
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p. 3348 - 3354
(2013/08/22)
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- RCAI-61 and related 6′-modified analogs of KRN7000: Their synthesis and bioactivity for mouse lymphocytes to produce interferon-γ in vivo
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We synthesized ten new analogs of 6′-modified KRN7000 (A): RCAI-58, 61, 64, 83, 85-87, 113, 119, and 125. They could be synthesized by α-selective galactosylation of ceramide 9 with the 6-modified d-galactopyranosyl fluorides (8a-8f) or l-arabinopyranosyl
- Tashiro, Takuya,Nakagawa, Ryusuke,Shigeura, Tomokuni,Watarai, Hiroshi,Taniguchi, Masaru,Mori, Kenji
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p. 3066 - 3079
(2013/07/28)
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- A highly efficient deprotection of the 2,2,2-trichloroethyl group at the anomeric oxygen of carbohydrates
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Commercially available zinc dust in the presence of ammonium chloride in acetonitrile at reflux removes the 2,2,2-trichloroethyl (TCE) group at anomeric centers with excellent yields (>95%) in short reaction times. This present method is easily implemented on substrates containing acyl and benzyl groups and large-scale reactions also proceed in high yield.
- Zhang, Jianbo,Fu, Jie,Si, Wenshuai,Wang, Xiaohu,Wang, Zhongfu,Tang, Jie
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experimental part
p. 2290 - 2293
(2011/11/12)
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- New method for regioselective glycosylation employing saccharide oxyanions
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As an alternative concept for glycosylation, the prior activation of acceptor hydroxy groups for selective glycosidic bond formation, was investigated to give complex oligosaccharides. Oxyanions obtained from partially protected saccharides were glycosylated by employing glycopyranosyl halides, and the regiochemical results were studied. Initially, partially methylated methyl-α-D-glucopyranosides were used as a model system to study the underlying mechanistic principles of base-promoted glycosylation. High regioselectivities and stereospecific glycosidic bond formations were achieved, and the scope of the methodology was extended with different perbenzylated glycosyl donors.
- Matwiejuk, Martin,Thiem, Joachim
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p. 5860 - 5878
(2011/11/06)
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- Versatile sugar derivatives for the synthesis of potential degradable hydrophilic-hydrophobic polyurethanes and polyureas
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Biodegradable polymers obtained from renewable natural sources are currently receiving increasing attention because they are an alternative to the traditional petroleum-based plastics. In the present communication we describe the synthesis of the diol mon
- De Paz, M. Violante,Aznar Moreno, José A.,Galbis, Juan A.
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p. 120 - 140
(2008/09/21)
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- Regioselective and diastereoselective amination of polybenzyl ethers using chlorosulfonyl isocyanate: Total syntheses of 1,4-dideoxy-1,4-imino-D-arabinitol and (-)-lentiginosine
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The total syntheses of DAB1 (1) and (-)-lentiginosine (2) were concisely accomplished from D-lyxose via regioselective and diastereoselective NHCbz introduction using CSI, chemoselective removal of the Cbz protection, and ring-closing metathesis as key steps.
- Kim, In Su,Zee, Ok Pyo,Jung, Young Hoon
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p. 4101 - 4104
(2007/10/03)
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- Stereoselective C-glycosylation reactions of pyranoses: The conformational preference and reactions of the mannosyl cation
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A systematic study of C-glycosylations of acetals related to mannose and other pyranoses was conducted. The C-5 alkoxyalkyl group provides only a modest influence on stereoselectivity. On the other hand, studies of pentopyranoses bearing alkoxy groups at
- Lucero, Claudia G.,Woerpel
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p. 2641 - 2647
(2007/10/03)
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- Synthesis and biological evaluation of aromatic analogues of conduritol F, L-chiro-inositol, and dihydroconduritol F structurally related to the amaryllidaceae anticancer constituents
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Pancratistatin is a potent anticancer natural product, whose clinical evaluation is hampered by the limited natural abundance and the stereochemically complex structure undermining practical chemical preparation. Fifteen aromatic analogues of conduritol F, L-chiro-inositol, and dihydroconduritol F that possess four of the six pancratistatin stereocenters have been synthesized and evaluated for anticancer activity. These compounds serve as truncated pancratistatin analogues lacking the lactam ring B, but retaining the crucial C10a-C10b bond with the correct stereochemistry. The lack of activity of these compounds provides further insight into pancratistatin's minimum structural requirements for cytotoxicity, particularly the criticality of the intact phenanthridone skeleton. Significantly, these series provide rare examples of simple aromatic conduritol and inositol analogues and, therefore, this study expands the chemistry and biology of these important classes of compounds.
- Kireev, Artem S.,Nadein, Oleg N.,Agustin, Vincent J.,Bush, Nancy E.,Evidente, Antonio,Manpadi, Madhuri,Ogasawara, Marcia A.,Rastogi, Shiva K.,Rogelj, Snezna,Shors, Scott T.,Kornienko, Alexander
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p. 5694 - 5707
(2007/10/03)
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- An approach to pancratistatins via ring-closing metathesis: Efficient synthesis of novel 1-aryl-1-deoxyconduritols F
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Structurally novel cyclitols, 1-aryl-1-deoxyconduritols F, were efficiently prepared from D-xylose, utilizing RCM as a key step. Various aromatic residues were incorporated in the cyclitol skeleton with total stereochemical control, utilizing a diastereoselective aryl cuprate addition to a γ-alkoxy enoate. The synthetic route establishes a firm foundation for a practical synthesis of the antitumor alkaloid pancratistatin and its aryl analogues.
- Nadein, Oleg N.,Kornienko, Alexander
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p. 831 - 834
(2007/10/03)
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- Molecular dynamics-based models explain the unexpected diastereoselectivity of the sharpless asymmetric dihydroxylation of allyl D- xylosides
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The catalytic asymmetric dihydroxylation of several allyl 2-O-benzyl-α- D-xylosides with AD-mix β and PYR(DHQD)2 shows almost no diastereofacial selectivity if the 3- and 4-OH groups are unprotected or acetylated. Acetal, benzyl ethers and benzoyl esters enhance the diastereoselectivity, in the opposite sense to that predicted by the 'AD mnemonic', which is completely lost using AD-mix α. In an attempt to understand this behaviour, computational studies of the asymmetric dihydroxylation (AD) of olefins using Sharpless' and Corey's catalysts have been carried out using molecular dynamics. A three-step algorithm was developed taking advantage of the enzyme-like behaviour of catalyst-olefin systems and applied using an ESFF force field. To validate our approach, the first sampling step procedure was then refined and performed using a modified CVFF force field. This led to a U-shaped model in good agreement with that proposed by Corey for the AD of allyl 4-methoxybenzoates, which brings to the fore a role for the methoxy group. This model also accounts for the observed enantioselectivity of styrene dihydroxylation. When applied to the AD of allyl xylosides using AD- mix β, our model accounts well for the observed diastereoselectivity. Both synthetic and modelling results confirmed that aromatic groups on the olefin could be involved in π-π stacking interactions with the aromatic rings of the catalyst and should be important, if not a prerequisite, to achieve high enantio- and diastereoselectivity.
- Moitessier, Nicolas,Maigret, Bernard,Chretien, Francoise,Chapleur, Yves
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p. 995 - 1005
(2007/10/03)
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- Modified α-D-Glcρ-(1-2)-α-D-Glcρ-(1-3)-α-D-Glcρ-analogues
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Disclosed is the trisaccharide α-D-Glcp-(1-2)-α-D-Glcp-(1-3)-α-D-Glcp and compounds related thereto as well as pharmaceutical compositions thereof.
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- Modified kojibiosides analogues
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Disclosed are novel analogues of kojibiose and pharmaceutical compositions comprising such analogues.
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- Immunostimulatory and antitumor activities of monoglycosylceramides having various sugar moieties
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Ten kinds of monoglycosylceramides (MonoCers), having the same ceramide portion and different sugar moieties, were synthesized and their immunostimulatory and antitumor activities were examined. The manner of combination between sugar and ceramide has been demonstrated to affect the manifestation of immunostimulatory and resultant antitumor activities of MonoCers, and in the case of D-MonoCers having the D-sugar, α-D-MonoCers (sugar combined to ceramide in an α-configuration) show stronger activities than β-D-MonoCers. Furthermore, the form of sugar, not the furanose-form but the pyranose-form, and the 2- and 4-hydroxyl groups of the pyranose-form of sugar, seemed to play an important role in the manifestation of the activities of α-D-MonoCers.
- Motoki,Morita,Kobayashi,Uchida,Akimoto,Fukushima,Koezuka
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p. 1487 - 1491
(2007/10/03)
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- A NOVEL PROCEDURE FOR THE PREPARATION OF 1-OH SUGAR DERIVATIVES USING 2-METHOXYETHYL GLYCOSIDES
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Treatment of benzyl-protected 2-methoxyethyl glycopyranosides with titanium tetrachloride followed by hydrolysis provides a new method for the preparation of the corresponding 1-OH sugar derivatives.The present method is shown to be useful for the prepara
- Morishima, Naohiko,Koto, Shinkiti,Kanemitsu, Kumi,Zen, Shonosuke
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p. 1189 - 1190
(2007/10/02)
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- Highly Stereoselective Grignard Reaction of an Aldopyranose: A Simple Synthesis of 6-Deoxy-D-idose from D-Xylose
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Grignard reaction of 2,3,4-tri-O-benzyl-D-xylopyranose yielded a single product with very high stereoselectivity.A threo relationship of the newly created chiral center with respect to C2 was established by converting the product into the δ-lactone of D-ido configuration, then to the unsaturated lactone of threo configuration.The result made possible a stereoselective synthesis of 6-deoxy-D-idose from D-xylose in a small number of steps.Models accounting for the high stereoselectivity in the Grignard reaction of aldoses are discussed.Keywords - Grignard reaction; stereoselectivity; configuration of unsaturated lactones; 2,3,4-tri-O-benzyl-D-xylose; 1-deoxy-D-sorbose; 6-deoxy-D-iono-1,5-lactone; 6-deoxy-D-idose; stereocontrol models
- Tsuda, Yoshisuke,Nunozawa, Tetsuji,Yoshimoto, Kimihiro
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p. 3223 - 3231
(2007/10/02)
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