Article
Chemistry, Multidisciplinary
Gael M. Vos, Yunfei Wu, Roosmarijn van der Woude, Robert P. de Vries, Geert-Jan Boons
Summary: This paper introduces a chemo-enzymatic strategy for synthesizing poly-N-acetyl lactosamines (polyLacNAc) in a regioselective manner. The strategy involves enzymatic assembly of oligo-LacNAc chains and modification at specific positions using traceless blocking groups. The methodology allows for the synthesis of polyLacNAc chains with various topologies.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Kazuki Inaba, Yuna Naito, Mina Tachibana, Kazunobu Toshima, Daisuke Takahashi
Summary: A regioselective and beta-stereospecific d-/l-arabinofuranosylation method has been developed for efficient synthesis of biologically active natural glycosides. The method showed high regioselectivity and yield with complete beta-stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Organic
Sebastian O. Simonetti, Teodoro S. Kaufman, Enrique L. Larghi
Summary: A comprehensive revision on natural and synthetic glycosylated quinolines, including synthesis, applications, natural products, and bioactivity data, is presented.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Mauro Paolini, Matteo Perini, Letizia Allari, Loris Tonidandel, Fabio Finato, Katia Guardini, Roberto Larcher
Summary: The study aims to create a national database of minor carbohydrates profiles and investigate the impact of geographical origin and vintages on the concentration of these compounds. 450 authentic Italian grape musts of different varieties were sampled and analyzed to study the influence of must concentration on the myo- and scyllo-inositol content. The proposed authenticity thresholds were found to be applicable to concentrated must (CM) and rectified concentrated must (RCM).
Article
Chemistry, Organic
Samim Sahaji, Pradip Shit, Anup Kumar Misra
Summary: A convergent [4+2] stereoselective block glycosylation strategy was developed for the synthesis of the hexasaccharide repeating unit of Klebsiella K19 strain's capsular polysaccharide with high yield. Temporary alkyl protecting group p-methoxybenzyl (PMB) was used and removed through glycosylation conditions. Thioglycoside served as a glycosyl acceptor in an orthogonal glycosylation reaction. TEMPO-mediated selective oxidation and thiophilic promoter N-iodosuccinimide (NIS) in combination with perchloric acid supported over silica (HClO4-SiO2) were used.
SYNTHESIS-STUTTGART
(2023)
Review
Chemistry, Multidisciplinary
Weidong Shang, Rong Shi, Dawen Niu
Summary: C-glycosides are important natural products and potential medicinal candidates. Nickel-catalyzed C-glycosylation reactions provide a promising strategy for their synthesis. Achieving stereoselective synthesis of alpha- and beta-C-glycosides has been a challenge, but recent developments in nickel-mediated strategies have addressed this problem. This review summarizes the advancements in diastereoselective C-glycosylation reactions and discusses the mechanistic understandings of these methods.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Swapan Kumar Jana, Pradip Shit, Anup Kumar Misra
Summary: In this study, the pentasaccharide repeating unit rich in 2-acetamidosugars corresponding to the O-antigenic polysaccharide from entero-pathogenic E. coli was successfully synthesized as the p-me-thoxyphenyl glycoside using a sequential glycosylation strategy. The key components of the synthetic strategy included regioselective glycosylation, use of a single monosaccharide intermediate in multiple glycosylations, and the use of thioglycosides as glycosyl donors in the presence of a combination of N-iodosuccinimide and perchloric acid supported over silica.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Physical
Juba Ghouilem, Christine Tran, Nicolas Grimblat, Pascal Retailleau, Mouad Alami, Vincent Gandon, Samir Messaoudi
Summary: This study presents a novel Pd-catalyzed reaction for anomeric C-H bond activation, leading to the synthesis of elusive C-(hetero)aryl glycosides with exclusive α-selectivity.
Article
Biochemistry & Molecular Biology
Laura Morelli, Laura Legnani, Silvia Ronchi, Laura Confalonieri, Daniela Imperio, Lucio Toma, Federica Compostella
Summary: This study investigated the role of cyclic 2,3-N,O-carbamate protecting group in directing the selectivity of mannosylation reactions of diacetone-D-glucose. Computational and experimental methods were used to show the preference of the formation of beta-adduct with mannosyl donors equipped with or without the 4,6-O-benzylidene protection. The results confirmed the preference for beta-adducts with an alpha/beta selectivity of 4:6.
CARBOHYDRATE RESEARCH
(2021)
Article
Biochemistry & Molecular Biology
Abhijit Rana, Pradip Shit, Anup Kumar Misra
Summary: A hexasaccharide repeating unit of Salmonella arizonae O62 was synthesized with high yield using a sequential glycosylation strategy. The desired compound was obtained with a minimum number of synthetic steps through successful regioselective glycosylation of the di-hydroxylated L-rhamnose moiety. Late stage regioselective oxidation of a primary hydroxyl group into carboxylic acid was achieved in the hexasaccharide derivative using TEMPO catalysis and [bis(acetoxy)iodo]benzene (BAIB) mediation. The glycosylation steps had high yields and stereochemical outcomes. The desired hexasaccharide was obtained in 7% overall yield in fourteen steps starting from suitably functionalized monosaccharide intermediates.
GLYCOCONJUGATE JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jiagen Li, Xuefeng Jiang
Summary: C-aryl glycosides, important carbohydrate derivatives in drug discovery, can resist hydrolysis from enzymes. This study establishes a synthesis method for 2-sulfur C-aryl glycals and 1,2-dihydrobenzofuran-fused C-aryl glycosides via interrupted Pummerer process, involving a sulfonium-tethered [3,3]-sigmatropic rearrangement. The protocol can be applied to a wide range of glycosyl and phenol substrates, and analogs of Dapagliflozin, Empagliflozin, and Ipragliflozin were successfully obtained.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jessica Jung, Lars Kaiser, Hans-Peter Deigner, Magnus S. Schmidt
Summary: In this study, bromoalkyl glycosides were successfully synthesized in microreactor scale by Fischer glycosylation, achieving yields between 24% and 40% after purification using various acidic catalysts and conditions. Some experiments demonstrated yields 180% higher than with previously known methods. Additionally, reversed-phase flash chromatography was shown to be more successful for purification, and longer bromoalcohols were found to be more compatible under these reaction conditions.
JOURNAL OF FLOW CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Divya Rajendran, Jebasingh Bhagavathsingh
Summary: The study presents a convenient synthesis of O-galactosylation by reacting Boc-activated diphenols with alpha-bromoacetogalactose. The protection of amine and diphenolic hydroxyl group enhances the formation of galactosylated products in two steps. The yields of beta-isomer L-DOPA glycoside reach 72-84% through Boc-activation of hydroxyl group in diphenols.
Article
Chemistry, Multidisciplinary
Wei Liu, Ziqiang Wang, Tayyab Gulzar, Xiaodong Zhang, Guoping Ding, Peng Xu, Biao Yu
Summary: We have revealed that EPP glycosides can be utilized as glycosylation donors through an unprecedented activation mechanism. We further report that EPP glycosides without the 3,5-dimethyl groups, previously installed to prevent side reactions, can also undergo effective glycosylation. By employing an EPP 2-azidoglucoside as a donor, we have successfully constructed the challenging alpha-GlcN-(1 -> 4)-GlcA linkage, leading to a heparin tri-saccharides precursor.
PURE AND APPLIED CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Antony J. Fairbanks
Summary: 2-Chloro-1,3-dimethylimidazolinium chloride (DMC) and its derivatives are valuable for selectively activating the anomeric center of unprotected reducing sugars in aqueous solution, allowing for efficient synthesis of glycosides and glycoconjugates without traditional protecting group manipulations. This mini-review explores the development and recent applications of DMC in protecting group-free synthesis.
CARBOHYDRATE RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Andres G. Santana, Laura Montalvillo-Jimenez, Laura Diaz-Casado, Enrique Mann, Jesus Jimenez-Barbero, Ana M. Gomez, Juan Luis Asensio
Summary: Glycosyl sulfoxides are important in the synthesis of complex oligosaccharides and have been used as model substrates. A systematic NMR study showed that glycosyl triflates play a crucial role in these glycosylations, despite the presence of the acceptor alcohol, and identified the formation of covalent donor/acceptor sulfonium adducts as the main competing reaction. This non-productive consumption of the acceptor could limit the reaction yield.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Biochemistry & Molecular Biology
Juan Ventura, Clara Uriel, Ana M. Gomez, Edurne Avellanal-Zaballa, Jorge Banuelos, Inmaculada Garcia-Moreno, Jose Cristobal Lopez
Summary: A convergent synthetic route for a tetrasaccharide related to PI-88, allowing a fluorescent BODIPY-label incorporation at the reducing-end, has been developed. The strategy showcases the utility of suitably-designed BODIPY dyes as glycosyl labels in synthetic strategies towards fluorescently-tagged oligosaccharides.
Article
Chemistry, Multidisciplinary
Ana M. Gomez, J. Cristobal Lopez
Summary: The combination of carbohydrates with BODIPY fluorophores leads to a family of BODIPY-carbohydrate hybrids, with benefits in imaging techniques and biocompatibility. This Account presents available methods for the synthesis of these hybrids, focusing on chemical transformations on the BODIPY core.
Article
Chemistry, Organic
Ana M. Gomez, Clara Uriel, Ainhoa Oliden-Sanchez, Jorge Banuelos, Inmaculada Garcia-Moreno, J. Cristobal Lopez
Summary: A novel, linker-free BODIPY-carbohydrate derivative has been efficiently obtained using a previously unreported Ferrier-type C-glycosylation method, resulting in hybrids with excellent photophysical properties and a weaker tendency to aggregate in concentrated water solutions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Clara Uriel, Ana M. Gomez, Enrique Garcia Martinez de la Hidalga, Jorge Banuelos, Inmaculada Garcia-Moreno, J. Cristobal Lopez
Summary: The hitherto unreported 2,6-dipropargyl-1,3,5,7-tetramethyl BODIPYs can be efficiently prepared and show improved photostability while retaining their inherent photophysical and photochemical properties. They can participate in efficient copper(I)-catalyzed azide-alkyne cycloaddition reactions to form all-BODIPY triads or conjugated BODIPYs.
Article
Biochemistry & Molecular Biology
Juan Ventura, Clara Uriel, Ana M. Gomez, J. Cristobal Lopez
Summary: Convergent synthetic routes to PI-88 tetra-and pentasaccharide-component analogues have been developed using regioselective glycosylations of mannose-polyol n-pentenyl glycosides (NPG) acceptors with 1,2-methyl orthoesters (MeOE) glycosyl donors.
CARBOHYDRATE RESEARCH
(2022)
Article
Biochemistry & Molecular Biology
Eva Maria Dominguez-Martin, Mariana Magalhaes, Ana Maria Diaz-Lanza, Mario P. Marques, Salvatore Princiotto, Ana M. Gomez, Thomas Efferth, Celia Cabral, Patricia Rijo
Summary: GB is a highly malignant form of primary astrocytoma. The development of new therapeutic approaches for GB is necessary due to the current treatment's limited efficacy and severe side effects. The plant genus Plectranthus, known for its abietane-type diterpenes with antitumor activity, shows potential as a source for developing new GB treatments. In this study, compounds were isolated from the acetonic extract of P. hadiensis stems and their antiglioblastoma activity was investigated. One of the isolated compounds, Roy, demonstrated strong antiproliferative effects against glioma tumor cells, indicating its potential as a lead compound for future therapeutic strategies against GB.
Article
Chemistry, Organic
Juan Ventura, Clara Uriel, Ana M. Gomez, Edurne Avellanal-Zaballa, Jorge Banuelos, Esther Rebollar, Inmaculada Garcia-Moreno, J. Cristobal Lopez
Summary: The presence of F or CN substituents at boron in BODIPYs has a significant impact on their reactivity. Tetramethyl B(CN)2-BODIPYs demonstrated enhanced reactivity in Knoevenagel condensations with aldehydes, while the corresponding BF2-BODIPYs can undergo selective aromatic electrophilic substitution (SEAr) reactions in the presence of the former. These (selective) reactions have been utilized in the synthesis of BODIPY dimers and tetramers with balanced fluorescence and singlet oxygen formation, as well as all-BODIPY trimers and heptamers with potential application as light-harvesting systems.
Article
Chemistry, Multidisciplinary
Ana M. M. Gomez, Juan Ventura, Clara Uriel, Jose Cristobal Lopez
Summary: Through the investigation of several methods, we found that BODIPY dyes can be used as aglycons through synthetic saccharide protocols. Stable and fluorescent water-soluble chromophores, which can address a challenge in molecular imaging, were synthesized using these methods.
PURE AND APPLIED CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Lydia Martinez-Parra, Marina Pinol-Cancer, Carlos Sanchez-Cano, Ana B. Miguel-Coello, Desire Di Silvio, Ana M. Gomez, Clara Uriel, Sandra Plaza-Garcia, Marta Gallego, Raquel Pazos, Hugo Groult, Marc Jeannin, Kalotina Geraki, Laura Fernandez-Mendez, Ainhize Urkola-Arsuaga, Maria Jesus Sanchez-Guisado, Juliana Carrillo-Romero, Wolfgang J. Parak, Maurizio Prato, Fernando Herranz, Jesus Ruiz-Cabello, Susana Carregal-Romero
Summary: Atherosclerosis is a complex disease with severe consequences. Existing diagnostic protocols lack specificity and fail to predict plaque vulnerability. However, emerging technologies, such as customized nanotechnological solutions, show promise in noninvasive imaging of atherosclerotic plaques. Our study demonstrates the effectiveness of Gd (III)-doped amorphous calcium carbonate nanoparticles in comparative studies of nanoparticle targeting for atherosclerosis.
