Article
Biochemistry & Molecular Biology
Nicolas Jouandon, Jana Hammoud, Alexandre Touron, Laetitia Bailly, Alexandra Le Foll, Antoine Y. P. Joosten, Thomas Lecourt
Summary: In this study, supercritical fluid chromatography coupled to high-resolution mass spectrometry (SFC-HRMS) was used to identify a chloro glycoside generated during the preparation of propargyl 1,2-orthoesters in dichloromethane. Further investigation revealed that the yield of this byproduct ranged from 20 to 40% depending on the source of anhydrous solvent, and tetrabutylammonium iodide enhanced this side reaction. Finally, a reliable procedure was developed in acetonitrile to synthesize these glycosyl donors from perbenzoylated bromo glycosides in the manno, gluco, and galacto series with yields of 63-74%.
CARBOHYDRATE RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Xiaoqian Li, Zhi Ma, Rongkun Liu, Mattan Hurevich, You Yang
Summary: A green and efficient photolabile protecting group (PPG)-mediated glycosidation approach for the synthesis of 2-deoxy-glycosides is reported. Multiple oNBC groups in the 2-deoxy-glycosides can be completely cleaved by irradiation at 365 nm, resulting in the desired 2-deoxy-glycosides in an efficient manner. Oligosaccharides with three to six oNBC groups are effectively achieved based on this PPG-mediated glycosidation approach.
CHINESE JOURNAL OF CHEMISTRY
(2021)
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
Javed, Ariza Khanam, Pintu Kumar Mandal
Summary: Both glycoconjugates and oligosaccharides play important roles in various biological processes. In this study, a new strategy for the synthesis of O/C-glycosides was reported using a versatile N-iodosuccinimide/trimethylsilyl triflate (NIS/TMSOTf) promoted glycosidation approach with a stable 3-phenyl-4-pentenoate glycosyl donor. The method showed high efficiency in synthesizing glycosides with free alcohols, silylated alcohols, and C-type nucleophile acceptors.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Tiantian Li, Jianjun Wang, Xinhao Zhu, Xin Zhou, Shaozi Sun, Peng Wang, Hongzhi Cao, Guangli Yu, Ming Li
Summary: Campylobacter jejuni, the leading cause of human diarrheal diseases, has been studied for potential antigens for innovative antibacterial glycoconjugation vaccines to address its high resistance. A novel method for synthesizing uncommon n-/L-6dHepp fluorides as glycosylating agents has been developed, allowing for the efficient construction of complex structures like the capsular polysaccharides of C. jejuni. This synthetic approach could serve as a rational starting point for developing synthetic vaccines combating Campylobacter infection.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Zhi Qiao, Dongwei Li, Jingru Gao, Zijiao Hou, Ningjie Yan, Ni Song, Peng Wang, Ming Li
Summary: This study describes a novel and efficient approach to synthesizing rare L-hexoses from readily available and inexpensive D-sugars. It involves the transformation of sugar rings through radical decarboxylative fluorination of uronic acids, allowing for the installation of anomeric hydroxymethyl group under mild conditions and C1-to-C5 switch. The power of this protocol is demonstrated by the assembly of a pentasaccharide repeating unit of Pseudomonas ATCC 31554 extracellular polysaccharide.
CHINESE JOURNAL OF CHEMISTRY
(2023)
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
Kazuki Kurahayashi, Kengo Hanaya, Takeshi Sugai, Go Hirai, Shuhei Higashibayashi
Summary: Metabolically stable C-glycosides play a crucial role in bioactive natural products, therapeutic agents, and biological probes. The development of synthetic methods for connecting glycosides and aglycons with strict stereocontrol is essential. In this study, a copper-catalyzed one-step borylation of glycosyl bromides to glycosyl boronates and a palladium-catalyzed cross-coupling of β-glycosyl borates with aryl bromides were successfully achieved, resulting in the synthesis of aryl β-C-glycosides.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Yashapal Singh, Scott A. Geringer, Alexei V. Demchenko
Summary: Advances in synthetic carbohydrate chemistry have improved access to common glycans, but challenges remain. Glycosyl halides play a crucial role in glycosylation.
Article
Chemistry, Organic
Eric M. Miller, Maciej A. Walczak
Summary: This study presents stereoselective C-arylation and etherification reactions of anomeric trifluoroborates derived from BMIDA esters, exhibiting high anomeric selectivities for 2-deoxysugars and showing a broad substrate scope, including disaccharides and trifluoroborates with free hydroxyl groups. This new class of carbohydrate reagents adds to the palette of anomeric nucleophile reagents suitable for efficient installation of C-C bonds.
Article
Biochemistry & Molecular Biology
Sonali Priyadarshini Parida, Tapaswini Das, Mohammed Ansar Ahemad, Tapaswini Pati, Seetaram Mohapatra, Sabita Nayak
Summary: In recent years, significant efforts have been devoted to the construction of C-glycosidic linkages in carbohydrate compounds, as they serve as important building blocks for many alkaloids and pharmaceutically active drug molecules. This review summarizes the recent developments in diverse synthesis of C-glycoside core between 2019 and 2022, with a focus on different catalytic strategies including transition-metal and metal-free approaches. The transition-metal catalyzed C-glycosylations are categorized into four sub classes: metal-based C-H activation, cross-coupling reactions, glycosyl radical intermediate-based processes, and others.
CARBOHYDRATE RESEARCH
(2023)
Article
Chemistry, Applied
Kameshwar Prasad, Ananay Sharma, Soumyaranjan Pati, Marc Taillefer, Florian Jaroschik, Srinivas Hotha
Summary: We report metal free conditions for the activation of alkynyl glycosyl carbonate donors using I-2/TMSOTf in stoichiometric quantities. The extrusion product was characterized as vinylidene iodide by single crystal X-ray analysis. The reaction conditions were suitable for the synthesis of various glycosides, purine/pyrimidine nucleosides, and a pentasaccharide repeating unit of Klebsiella pneumoniae (O-3 antigen).
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Biochemistry & Molecular Biology
Maniyamma Aswathy, Balan Abhijith, Ravi S. Lankalapalli, Kokkuvayil V. Radhakrishnan
Summary: In this study, we utilized the organic Bronsted acid PCCP to catalyze the glycosidation reactions of glucose and galactose. Different protecting groups led to different stereoselective products.
CARBOHYDRATE RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Carla Obradors, Benjamin Mitschke, Miles H. Aukland, Markus Leutzsch, Oleg Grossmann, Sebastian Brunen, Sebastian A. Schwengers, Benjamin List
Summary: Since early 2020, scientists have been striving to find effective solutions to combat SARS-CoV-2, focusing on developing reliable vaccines and repurposing drugs. However, the current synthetic routes for Remdesivir, the most widely used therapeutic during the early stages of infection, face challenges in cost-effective supply to patients. In this study, researchers have developed a straightforward method for adding (hetero)arenes to unprotected sugars, significantly expediting the synthesis of Remdesivir precursor GS-441524.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Shuang An, Quanquan Wang, Wanjun Zhu, Qikai Sun, Gang He, Gong Chen
Summary: A new protocol for glycosylation using glycosyl chloride donors under palladium-catalyzed conditions has been developed. This method is operationally simple, robust, and enables efficient synthesis of various glycosides, including N-ribonucleoside analogs.
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.