Article
Chemistry, Organic
Jianpeng Chen, Yu Tang, Biao Yu
Summary: A mild glycosylation method using glycosyl 1-methylimidazole-2-carboxylates has been developed, with the reaction being promoted by metal triflates and triflimides, especially Cu(OTf)(2). The reaction is initiated by coordination of the glycosyl ester donor with the metal cation assisted by the adjacent 1-methylimidazole chelating group.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Shiyang Xu, Wei Zhang, Caiyi Li, Yanjing Li, Hongxin Zeng, Yingwei Wang, Yang Zhang, Dawen Niu
Summary: We present a method for generating glycosyl radicals under highly acidic conditions. This method utilizes glycosyl sulfinates as radical precursors, which are stable solids and can be easily prepared from commercial starting materials. The method allows for direct installation of glycosyl units onto pyridine rings through the Minisci reaction. We showcase the utility of the method in the late-stage modification of complex drug molecules, including camptothecin. Experimental studies provide insight into the reaction mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Quanquan Wang, Wanjun Zhu, Qikai Sun, Gang He, Gong Chen
Summary: A novel Pd-catalyzed ortho-directed C-H glycosylation reaction using N-linked bidentate auxiliaries has been developed for efficient synthesis of C-aryl glycosides with high yield and selectivity. This method allows for installation of a wide range of pyranose and furanose moieties on various substrates and facile installation and removal of the auxiliaries under mild conditions.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Yu Tang, D. Prabhakar Reddy, Biao Yu
Summary: A new dehydrative glycosylation protocol involving selective activation of glycosyl hemiacetals has been developed, which operates under mild basic conditions and allows for the synthesis of symmetrical 1,1'-disaccharides in high yields.
Article
Chemistry, Multidisciplinary
Jun Wu, Nikolaos Kaplaneris, Julia Poehlmann, Takuya Michiyuki, Binbin Yuan, Lutz Ackermann
Summary: The prevalence of C-aryl glycosides in biologically active natural products and approved drugs has motivated the development of efficient synthesis strategies. Palladium catalysts with prefunctionalized substrates have been commonly used, while ruthenium-catalyzed C-aryl glycoside synthesis has been challenging. In this study, a versatile ruthenium(II)-catalyzed meta-C-H glycosylation method was disclosed, allowing for the synthesis of meta-C-aryl glycosides from readily available glycosyl halide donors. The ruthenium catalysis exhibited mild reaction conditions, exceptional levels of anomeric selectivity, and exclusive meta-site-selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Katreen A. F. Banisalman, Athina Polykandritou, Francis M. Barnieh, Goreti Ribeiro Morais, Robert A. Falconer
Summary: Glycosylation is commonly used to mimic post-translational modifications and modify the properties of peptides. This study introduces a simple and chemoselective method to prepare disulfide-linked glycopeptides. The procedure is highly reactive with cysteine residues in peptides and can be used with unprotected carbohydrates.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Hao Zuo, Chen Zhang, Yang Zhang, Dawen Niu
Summary: A simple and general method for fully unprotected, stereoselective glycosylation of carboxylic acids was developed using bench-stable allyl glycosyl sulfones as donors. The reaction, conducted under basic conditions, showed high efficiencies and selectivities. Both the donor activation stage and the glycosidic bond forming stage were compatible with free hydroxyl groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Zhi Qiao, Peng Wang, Jingxuan Ni, Dongwei Li, Yao Sun, Tiantian Li, Ming Li
Summary: This study presents a novel catalytic glycosylation reaction using disarmed glycosyl ortho-isopropenylphenylacetates (GIPPAs) and ortho-isopropenylbenzyl thioglycosides as glycosylating agents. Various O-, S-, and C-nucleophiles can be efficiently glycosylated under mild conditions. This work provides new glycosyl ester and thioglycoside donors for acid-catalyzed glycosylation.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Food Science & Technology
Yuqing Tian, Wei Xu, Cuie Guang, Wenli Zhang, Wanmeng Mu
Summary: This review provides a comprehensive overview of the O-glycosylation of flavonoids catalyzed by glycoside hydrolases, including their catalytic mechanism, reaction conditions, and physicochemical properties of the product flavonoid glycosides. This biosynthesis approach offers a practical method to enhance glycodiversification due to its cheap glycosyl donor substrates and high yields.
CRITICAL REVIEWS IN FOOD SCIENCE AND NUTRITION
(2023)
Article
Chemistry, Multidisciplinary
Thomas Hansen, Tim P. Ofman, Joey G. C. Vlaming, Ivan A. Gagarinov, Jessey van Beek, Tessa A. Gote, Jacoba M. Tichem, Gijs Ruijgrok, Herman S. Overkleeft, Dmitri V. Filippov, Gijsbert A. van der Marel, Jeroen D. C. Codee
Summary: By systematically studying the reactivity-stereoselectivity relationships of caryophyllose donor and acceptor glycosides, using experimental and computational techniques, we were able to design carbohydrate building blocks with the necessary properties to assemble mycobacterial lipooligosaccharide fragments of M. marinum.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Manami Semba, Shinji Takamatsu, Sachiko Komazawa-Sakon, Eiji Miyoshi, Chiharu Nishiyama, Hiroyasu Nakano, Kenta Moriwaki
Summary: The study identified proscillaridin A as a promising agent that enhances the anti-cancer efficacy of TRAIL therapeutics, particularly in colon cancer cells.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Review
Agriculture, Multidisciplinary
Michael Kotik, Natalia Kulik, Katerina Valentova
Summary: Flavonoids and their glycosides are abundant in plant-based foods and studying the glycosylation process is important for understanding their bioactivities and applications.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Naresh Bhuma, Ludivine Lebedel, Hiroki Yamashita, Yutaka Shimizu, Zahra Abada, Ana Arda, Jerome Desire, Bastien Michelet, Agnes Martin-Mingot, Ali Abou-Hassan, Masahiro Takumi, Jerome Marrot, Jesus Jimenez-Barbero, Aiichiro Nagaki, Yves Bleriot, Sebastien Thibaudeau
Summary: Ferrier's research in 1962 on the transformation of glycals into unsaturated glycosyl derivatives involved an alpha,beta unsaturated glycosyl cation. Through NMR-based structural analysis and DFT calculations, this elusive ionic species was characterized, leading to the synthesis of unsaturated nitrogen-containing C-aryl glycosides and C-alkyl glycosides under different conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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.
Review
Plant Sciences
Richard Strasser, Georg Seifert, Monika S. Doblin, Kim L. Johnson, Colin Ruprecht, Fabian Pfrengle, Antony Bacic, Jose M. Estevez
Summary: Glycosylation is a crucial modification process that can alter the biological function of proteins and lipids, affecting the development and physiology of an organism. While challenges remain in understanding plant glycosylation, high throughput approaches may help to address these gaps, revolutionizing the identification and characterization of unknown plant glycosyltransferases and hydrolases.
FRONTIERS IN PLANT SCIENCE
(2021)
Article
Oncology
Ahmed Elgehama, Yixuan Wang, Ying Yu, Lin Zhou, Zhixiu Chen, Liwei Wang, Lijun Sun, Jian Gao, Biao Yu, Yan Shen, Qiang Xu
Summary: This study unravels the action mechanism of PTP1B in stabilizing Bcr-Abl1 protein and indicates that the PTP1B-Bcr-Abl1 interaction might be one of druggable targets for TKI-resistant CML with point mutations.
Article
Biochemistry & Molecular Biology
Zhi Ma, Yi Hu, Xiaona Li, Rongkun Liu, E. Xia, Peng Xu, You Yang
Summary: In this study, a SPhosAuNTf2-promoted DMF-modulated glycosylation approach was developed for the highly alpha-selective synthesis of various linkage types of alpha-glucans using glycosyl (Z)-ynenoates as donors. The substituent groups were found to play a significant role in the alpha-selective glucosylation reactions. The approach was effectively applied to the stereospecific synthesis of the alpha-1,6-linked triglucoside.
CARBOHYDRATE RESEARCH
(2023)
Article
Chemistry, Inorganic & Nuclear
Chang Zheng, Yu Tang, Biao Yu
Summary: Twelve protonated and deuterated gold(I) complexes with phosphorous triamide-type ligands were synthesized and characterized. An elusive Au-H(D) interaction between the phosphine ligand and the central gold atom was observed. Isotopic polymorphism was observed in one of the complexes in the crystal structure. These complexes showed high catalytic activity in glycosylation reactions.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Xin Zhang, Peng Xu, Biao Yu
Summary: Chemical synthesis of a hexasaccharide relevant to colanic acid, which contains a high level of polyanionic and acetyl decoration, has been successfully achieved using stereoselective glycosylation and efficient installation of O-acetyl and pyruvate residues.
Article
Chemistry, Multidisciplinary
Youxi Chen, Guozhi Xiao, Dapeng Zhu, Biao Yu
Summary: Sepositoside A is a prototypical cyclic steroid glycoside with a hybrid 16-membered ring composed of the steroid skeleton and a 1,2-trans-linked trisaccharide. We report a convenient method to construct the strained 16-membered ring via Au(I)-catalyzed intramolecular addition of alcohol to epoxide, leading to two simplified analogues. Although a similar macroetherification in relevant steroid trisaccharides has been extensively studied, it has failed to provide the macrocyclic skeleton of Sepositoside A.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Bingfeng Shi, Youxi Chen, Mingyu Geng, Dapeng Zhu, Biao Yu
Summary: Sepositoside A is a major cyclic steroid glycoside found in starfishes, featuring a strained 16-membered ring formed by a linear trisaccharide tethered to C3 and C6 of the steroid aglycone. Attempts to synthesize the desired steroid-pyranose etherate linkage and assemble the glycans stepwise have been unsuccessful. Alternative approaches to construct the steroid-pyranose etherate linkage will be explored in future articles.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Dapeng Zhu, Mingyu Geng, Dacheng Shen, Biao Yu
Summary: This article presents a formal total synthesis study of starfish cyclic steroid glycosides 1 and 2 isolated from the Pacific starfish Echinaster Luzonicus. The synthetic route is highly modular and versatile, involving Au(I)-catalyzed intramolecular glycosylation for constructing the 16-membered macrocycles, efficient installation of unsaturated sugar moieties using ortho-hexynylbenzoates, post-oxidation elaboration of the glucuronic acid unit, and de novo synthesis of the ether-linked pyranose unit.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xiaojuan Zhang, Peng Xu, Zhengbing Zhou, Yazhou Zhang, Biao Yu, Yugen Zhu
Summary: Due to the complexity and diversity of carbohydrates, efficient methods for homogeneous oligosaccharides are limited. Chemical synthesis is a reliable approach for accessing homogeneous samples, relying on glycosylation reactions. This study presents a novel leaving group, 8-phenylethynyl-1-naphthoate, which enables efficient glycosylation reactions under mild gold(I)-catalysis. The unique base-stability of the anomeric naphthoate group allows compatibility with various chemical transformations, and the protocol allows for minimally protected glycosylation processes. Mechanistic studies explain the characteristics of 8-phenylethynyl-1-naphthoate.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Bei-Bei Zhan, Kai-Sheng Xie, Qian Zhu, Weiping Zhou, Dapeng Zhu, Biao Yu
Summary: A Cu-(OTf)(2)-catalyzed glycosylation protocol using glycosyl ortho-N-phthalimidoylpropynyl benzoates(NPPBs) as donors was developed, which exhibits an inexpensive catalyst, convenient conditions, high to excellent yields, and a broad substrate scope. Mechanistic studies showed the formation of an isochromen-4-ylcopper-(II) intermediate upon leaving group departure.
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
Chemistry, Multidisciplinary
Xiaona Li, Cristina Di Carluccio, He Miao, Lvfeng Zhang, Jintao Shang, Antonio Molinaro, Peng Xu, Alba Silipo, Biao Yu, You Yang
Summary: We report a promoter-controlled cycloglycosylation approach for the synthesis of cyclic α-(1→6)-linked mannosides up to a length of 32 units. The method relies on the role of a gold(I) complex in the proper preorganization of the ultra-large cyclic transition state. NMR experiments and a computational study revealed that the cyclic 2-mer, 4-mer, 8-mer, 16-mer, and 32-mer mannosides adopted different conformational states and shapes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Yan Xia, Yingjie Wang, Zhaolun Zhang, Tayyab Gulzar, Yuqi Lin, Jing Wang, Dapeng Zhu, Biao Yu
Summary: The synthesis of neopetrosins A and C, two 2-indolyl C-a-D- mannopyranosides, and their congeners has been achieved via a direct Ni/photoredox-catalyzed reductive coupling of 3-methoxycarbonyl-2-iodo-1H-indoles with pyranosyl bromides.
Article
Chemistry, Organic
Wei Liu, Zhifei Hu, Peng Xu, Biao Yu
Summary: Here, we presented a convenient procedure to prepare EPP glycosides and their application in the synthesis of the clinically approved anticoagulant fondaparinux. Additionally, we successfully achieved the synthesis of heparin-like tetrasaccharides using EPP glycosides in a one-pot orthogonal glycosylation reaction.
Article
Chemistry, Multidisciplinary
Wu Hou, Xin Cao, Peng Xu, Biao Yu
Summary: In this study, the synthesis of two tetranorditerpenoid dilactones, Wentilactones A and B, with promising antitumor activities is reported for the first time. The synthesis involves the use of a common precursor, 3 beta-hydroxydilactone 6, derived from (S)-Wieland-Miescher ketone, and allows for easy modification on the A-ring, resulting in compounds such as CJ-1445, asperolide B, and an unnamed natural congener 4.
CHEMICAL COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Peng Xu, Biao Yu
Summary: Glycans, the most abundant organic polymers in nature, hold great significance in studying condensed matter chemistry and their synthesis.
PROGRESS IN CHEMISTRY
(2022)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
