Article
Chemistry, Organic
Akito Shibuya, Moeko Kato, Asuka Saito, Sujit Manmode, Naoto Nishikori, Toshiyuki Itoh, Aiichiro Nagaki, Toshiki Nokami
Summary: This study found that the stability of glycosyl dioxalenium ions can be enhanced by introducing tert-butyldiphenylsilyl group at 6-OH, allowing reactions to be performed at elevated temperatures. NMR and VT-NMR measurements revealed the impact of protecting groups on the stability of intermediates, leading to the successful synthesis of a trisaccharide with a glucoside β-1,6 linkage.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Ze-Yu Tian, Zeng-Hui Lin, Cheng-Pan Zhang
Summary: A selective formal C-H/C-H cross-coupling of azoles and (hetero)arenes was established using arylsulfonium intermediates under transition-metal catalysis, providing a variety of 2-(hetero)aryl azoles in good to excellent yields. The advantages of this reaction include mild reaction conditions, good functional group tolerance, a wide substrate scope, high regio- and chemoselectivity, one-pot procedures, and late-stage functionalization of complex molecules without the use of oxidants, offering a promising strategy for transition-metal-catalyzed C-H arylation of azoles.
Article
Chemistry, Multidisciplinary
Weitao Yan, Mingwen Zheng, Peihsuan Chuang, Hao Sun, Shiping Wang, Chunfa Xu, Fen-Er Chen
Summary: A highly efficient coupling of glycosyl stannanes and sulfonium salts enabled by synergistic Pd/Cu catalysis has been developed for the construction of C-aryl/alkenyl glycals. This protocol demonstrates wide functional group tolerance and the one-pot formal C-H glycosylation starting from arene. Additionally, the successful gram-scale reaction indicates the high applicability of this method.
CHINESE CHEMICAL LETTERS
(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)
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, Applied
Yi Zhu, Lun Li, Yuchao Zhang, Yang Ou, Jingyan Zhang, Yusuf Yagci, Ren Liu
Summary: This work reports the synthesis and characterization of sulfonium salt photoinitiators (PIs) with a coumarin skeleton. The photochemical and photophysical properties of the PIs were investigated through spectroscopic and computational investigations. The PIs showed excellent photolysis and initiating efficiency for various photopolymerization reactions without any additives in the UV and visible regions. The solubility and activity of the active species could be controlled by adjusting the length of the aliphatic chain on the sulfur atom. These PIs are anticipated to have broad applications in photopolymerization processes.
PROGRESS IN ORGANIC COATINGS
(2023)
Review
Chemistry, Multidisciplinary
Hendrik F. T. Klare, Lena Albers, Lars Suesse, Sebastian Keess, Thomas Mueller, Martin Oestreich
Summary: The history of silyl cations had a dramatic beginning, as they were once considered impossible to isolate in the condensed phase. However, their actual characterization in solution and solid state changed this perception, leading to wide acceptance and promising applications in synthetic chemistry. Silyl cations are known for their enormous electrophilicity and reactivity, making them key compounds in various chemical reactions.
Article
Chemistry, Organic
Sabrina de Lorenzo, Lauriane Pillet, David Lim, Francesca Paradisi
Summary: A one-pot synthesis method for glycosyl benzoates from unprotected sugars in water using 2-chloro-1,3-dimethylimidazolium chloride, thiobenzoic acid, and triethylamine was developed. These glycosyl donors were found to be excellent substrates for both wild-type and mutant glycosidases. The hydrolysis of β-glucosyl benzoate by the GH1 β-glucosidase from Halothermothrix orenii was demonstrated, and the donor's superiority in thioligase-mediated glycosylation was shown with high conversions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
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
Chemistry, Organic
Daiki Takeda, Makoto Yoritate, Hiroki Yasutomi, Suzuka Chiba, Takahiro Moriyama, Atsushi Yokoo, Kazuteru Usui, Go Hirai
Summary: C-Glycosides are metabolically stable mimics of natural O-glycosides, synthesized through stereoinvertive sp(3)-sp(2) cross-coupling reactions using a photoredox/nickel dual catalytic system. The hydrogenation of vinyl C-glycosides leads to C-linked 2'-deoxydisaccharide analogues.
Article
Chemistry, Organic
Xiaoyu Li, Qianyun Zhang, Yuanyuan Xie, Hongwei Zhou
Summary: A protocol was developed for the synthesis of polysubstituted phenols and functionalized carbocycles via the acylation of electron-poor alkenyl sulfoxides, using readily available starting materials and mild reaction conditions. The plausible mechanism behind this transformation was also investigated.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Yaping Zhang, Hongkun Xu, Leying Jiang, Zhaodi Liu, Chenshan Lian, Xiaofeng Ding, Chuan Wan, Na Liu, Yuena Wang, Zhiqiang Yu, Lizhi Zhu, Feng Yin, Zigang Li
Summary: This study demonstrates that DNA nanodevices with sulfonium centers can provide a precise, biocompatible, and effective co-delivery vaccine platform for tumor immunotherapy and prevention, enhancing immune responses and potentially inhibiting tumor growth.
Article
Nanoscience & Nanotechnology
Zhefei Yang, Jing Zhao, Todd Emrick
Summary: The synthesis and application of sulfothetin-containing polymer zwitterions for stabilizing emulsion droplets and capturing/transporting nanoparticles in aqueous fluid were discussed. These multifunctional copolymers embed reactive functionality in the zwitterionic framework, contributing to both droplet stabilization and interfacial reactivity. The successful NP pickup experiments highlighted the importance of the available reactivity of both the electrophilic ST components and nucleophilic NPs, along with solution pH and extent of NP functionality.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Polymer Science
Benjamin A. Suslick, Aliza N. Yazdani, Morgan M. Cencer, Justine E. Paul, Nil A. Parikh, Katherine J. Stawiasz, Isabel P. S. Qamar, Nancy R. Sottos, Jeffrey S. Moore
Summary: Frontal ring-opening metathesis polymerization (FROMP) catalyzed by Grubbs-type Ru complexes allows for the rapid and energy-efficient synthesis of high-performance structural plastics. By using a thermally latent bis-N-heterocyclic carbene complex and Cu-I coreagents, the system can be primed for rapid reactivity after thermal initiation, leading to the formation of robust resins with enhanced stability. Additionally, controlling the Cu to Ru ratio significantly impacts the reaction velocity and temperature, as well as the glass-transition temperature of the resulting polymers.
Review
Chemistry, Multidisciplinary
Leendert van Dalsen, Rachel E. Brown, James A. Rossi-Ashton, David J. Procter
Summary: The photoactivation of electron donor-acceptor complexes is a sustainable and versatile strategy for generating radicals. However, the electronic constraints of the donor and acceptor components can limit the range of radicals that can be generated. By using sulfonium salts in electron donor-acceptor complexation, radicals can now be generated from native functionality. This approach relaxes the electronic constraints and expands the range of radicals that can be generated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biotechnology & Applied Microbiology
Yuki Sasaki, Masahiro Komeno, Akihiro Ishiwata, Ayako Horigome, Toshitaka Odamaki, Jin-Zhong Xiao, Katsunori Tanaka, Yukishige Ito, Kanefumi Kitahara, Hisashi Ashida, Kiyotaka Fujita
Summary: Gum arabic arabinogalactan protein (AGP) can be effectively degraded by the cooperative action of GAfase, exo-beta 1,3-galactanase (Bl1,3Gal), and BlArafE, leading to the production of alpha-L-Rhap-(1 -> 4)-beta-D-GlcpA-(1-6)-beta-D-Galp-(1 -> 6)-D-Gal tetrasaccharide. This oligosaccharide can be utilized by commensal bacteria, potentially facilitating cross-feeding interactions between bifidobacteria and other gut microbial groups.
APPLIED AND ENVIRONMENTAL MICROBIOLOGY
(2022)
Article
Biochemistry & Molecular Biology
Midori Ikezaki, Kazuchika Nishitsuji, Ko Matsumura, Shino Manabe, Yukinao Shibukawa, Yoshinao Wada, Yukishige Ito, Yoshito Ihara
Summary: This study investigated the effects of C-mannosylation on the biological function of WSPW peptides and found that C-mannosylated WSPW peptides could interact with actinin-4, influencing the expression and subcellular localization of E-cadherin in cells.
Article
Biochemistry & Molecular Biology
Wataru Miyanishi, Makoto Ojika, Dai Akase, Misako Aida, Yasuhiro Igarashi, Yukishige Ito, Yu Nakagawa
Summary: The study found that attachment of 2-aminoethanol to the carboxy group of PRM-A significantly suppressed aggregation, and the prepared amide derivatives not only bound to Man without aggregation but also exhibited antifungal activity.
BIOORGANIC & MEDICINAL CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Kazuchika Nishitsuji, Midori Ikezaki, Shino Manabe, Kenji Uchimura, Yukishige Ito, Yoshito Ihara
Summary: C-Mannosylation affects the biological functions of proteins, especially in thrombospondin 1 repeats. C-Mannosylated WSPW peptide inhibits TGF-beta-mediated synaptogenesis by suppressing Smad 2 activation. The molecular details of how C-mannosylation affects the biological functions of WxxW motifs require further study for clarification.
GLYCOCONJUGATE JOURNAL
(2022)
Article
Biochemistry & Molecular Biology
Takashi Kikuma, Haruka Ibuki, Masaya Nakamoto, Akira Seko, Yukishige Ito, Yoichi Takeda
Summary: It has been discovered that EDEM3 plays a significant role in the protein quality control in the endoplasmic reticulum (ER), by converting specific glycans into other types of glycans. Additionally, the activity of EDEM3 is enhanced through interaction with ERp46. This study provides new insights into the enzymatic properties of EDEM3 and the use of artificial glycan substrates to study ERAD mechanisms.
BIOCHEMICAL AND BIOPHYSICAL RESEARCH COMMUNICATIONS
(2022)
Article
Biochemistry & Molecular Biology
Sayaka Higashi, Yuki Imamura, Takashi Kikuma, Takahiro Matoba, Saya Orita, Yoshiki Yamaguchi, Yukishige Ito, Yoichi Takeda
Summary: The details of the complex formation between SelenoF and HUGT1 in the endoplasmic reticulum glycoprotein quality control system are still unclear. This study used co-transfection and crosslinking experiments to reveal the binding position of SelenoF to HUGT1, further elucidating the function of SelenoF.
Article
Chemistry, Multidisciplinary
Junpei Abe, Yoichi Takeda, Takashi Kikuma, Yasuhiko Kizuka, Hiroyuki Kajiura, Yasuhiro Kajihara, Yukishige Ito
Summary: UDP-Glc：glycoprotein glucosyltransferase (UGGT) plays a central role in maintaining the quality control of correctly folded N-glycoproteins in the endoplasmic reticulum (ER). However, a selective and potent inhibitor against UGGT has not been identified. In this study, we report squaryl group-modified UDP analogs as potential UGGT inhibitors, with one compound showing the highest potency and suggesting a candidate for further optimization.
CHEMICAL COMMUNICATIONS
(2023)
Review
Biochemistry & Molecular Biology
Kazuchika Nishitsuji, Midori Ikezaki, Shino Manabe, Yoshito Ihara
Summary: Protein C-mannosylation is a unique type of protein glycosylation where a single α-mannose is attached to the indole C2 of tryptophan through a C-C bond. Dpy-19, DPY19L1, and DPY19L3 are genes encoding C-mannosyltransferases. Consensus motifs of C-mannosylation can be found in thrombospondin type 1 repeat and cytokine receptor type I families, suggesting critical roles of this modification in protein folding, sorting, and secretion.
TRENDS IN GLYCOSCIENCE AND GLYCOTECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Methanee Hiranyakorn, Shogo Iwamoto, Asako Hoshinoo, Ryo Tsumura, Hiroki Takashima, Masahiro Yasunaga, Shino Manabe
Summary: N-Linked glycosylation on IgG has a significant impact on antibody functions. The relationship between N-glycan structure and Fc gamma RIIIa binding affinity affects ADCC activity. The study shows that the N-glycan structure and length on IgGs, Fc fragments, and ADCs influence the retention time in column chromatography, suggesting their impact on Fc gamma RIIIa binding and ADCC activity.
Article
Biochemistry & Molecular Biology
Yahani P. Jayasinghe, Michael T. Banco, Jared J. Lindenberger, Lorenza Favrot, Zuzana Palcekova, Mary Jackson, Shino Manabe, Donald R. Ronning
Summary: This study further characterized the functionality of Mycothiol S-transferase (MST) in Mycobacterium tuberculosis and examined its role in xenobiotic stress. The results showed that MST is stabilized by the binding of Mycothiol (MSH) and the presence of metal ions. However, cell-based experiments failed to provide evidence for the involvement of MST in the processing of rifampicin or isoniazid, suggesting the need for further research to identify the acceptors of the enzyme and better define its biological role.
RSC MEDICINAL CHEMISTRY
(2023)
Meeting Abstract
Oncology
Hiroki Takashima, Yoshikatsu Koga, Shino Manabe, Kazunobu Ohnuki, Ryo Tsumura, Takahiro Anzai, Yang Wang, Xiaojie Yin, Akihiro Nambu, Nozomi Sato, Sachiko Usuda, Hiromitsu Haba, Hirofumi Fujii, Yasuhiro Matsumura, Masahiro Yasunaga
Meeting Abstract
Oncology
Shiqi Yang, Masahiro Yasunaga, Shino Manabe
Article
Biochemistry & Molecular Biology
Shun Maruyama, Kota Sawano, Satoko Amaki, Takehiro Suzuki, Satoru Narita, Kenta Kimura, Takatoshi Arakawa, Chihaya Yamada, Yukishige Ito, Naoshi Dohmae, Kiyotaka Fujita, Akihiro Ishiwata, Shinya Fushinobu
Summary: This study investigated the catalytic mechanism and substrate binding structure of the beta-l-arabinofuranosidase HypBA1 from Bifidobacterium longum. Zn2+ ion and cysteine were found to play key roles in catalysis, and the mode of substrate binding affected the catalytic activity.
