Article
Chemistry, Multidisciplinary
Hui Liu, Zhi-Fen Liang, Han-Jian Liu, Jin-Xi Liao, Li-Jun Zhong, Yuan-Hong Tu, Qing-Ju Zhang, Bin Xiong, Jian-Song Sun
Summary: With easily accessible and operator-friendly reagents, shelf-stable ortho-methoxycarbonylethynylphenyl thioglycosides were efficiently prepared. A novel glycosylation protocol utilizing Au(I) or Cu(II) complexes was established, allowing for expanded substrate scope and versatility in glycoside synthesis. The mechanism and side product formation of C-glycosylation were also investigated.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Zoe Beato, Xiangming Zhu
Summary: A new method for synthesizing superarmed thioglycosides via the ring opening of 1,2-orthoesters is reported, ensuring the necessary stereochemistry and using trimethylsilyl thioethers as sulfur nucleophiles to avoid the use of unpleasant free thiols.
Article
Chemistry, Organic
Dirk Leifert, Frauke Weidlich, Florin Adler, Constantin G. Daniliuc, Fatmah A. Alasmary, Armido Studer
Summary: A radical cascade reaction to access 2,3-disubstituted indoles via acylation or trifluoromethylation of ortho-alkynylphenyl isonitriles is described. The reaction involves forming two C-C bonds and one C-O bond using an inexpensive oxidant and catalytic copper or iron salt. Starting isonitriles are readily available, and commercially available aldehydes and fluoromethylation reagents are used as reactants, demonstrating high functional group tolerance and successful synthesis of a series of 2,3-disubstituted indoles.
Article
Chemistry, Multidisciplinary
Yafei Cao, Minmin Zhou, Run-Ze Mao, You Zou, Feng Xia, Da-Ke Liu, Jianhui Liu, Qin Li, De-Cai Xiong, Xin-Shan Ye
Summary: A new glycosylation method using visible light and 3,5-dimethoxyphenyl glycoside as the donor was developed, which delivers O-glycosides and N-glycosides in moderate to excellent yields with a wide range of O-nucleophiles and nucleobases as the glycosyl acceptors.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Wahyu S. Putro, Yusuke Munakata, Seiichiro Ijima, Shinji Shigeyasu, Satoshi Hamura, Seiji Matsumoto, Takayoshi Mishima, Keiichi Tomishige, Jun-Chul Choi, Norihisa Fukaya
Summary: The combination of CeO2 catalyst and ethanol effectively promotes the direct synthesis of diethyl carbonate from CO2 and an orthoester. Optimized conditions yield high productivity, with orthoesters bearing longer alkyl substituents leading to higher DEC yields in the presence of ethanol. Aromatic and halide moieties in orthoesters negatively impact DEC formation.
JOURNAL OF CO2 UTILIZATION
(2022)
Article
Chemistry, Multidisciplinary
Karim Muratov, Fabien Gagosz
Summary: In this research, a new class of structurally simple and easily accessible bulky tri-(ortho-biaryl)phosphine ligands and their gold(I) complexes were synthesized. Their confined nature was demonstrated through X-ray diffraction analysis and comparative evaluation. Despite their notable steric congestion, these complexes exhibited remarkable catalytic activities and unusual selectivities, making them unique in the field of synthetic homogeneous gold catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Guang-Jing Feng, Tao Luo, Yang-Fan Guo, Chun-Yang Liu, Hai Dong
Summary: A green method using sodium alkanethiolates instead of alkyl mercaptans and trifluoromethanesulfonic acid in nonpolar solvents is developed for synthesizing 1-thioalkyl glycosides and 1,2-cis-alpha-thioglycosides under mild conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Nilay Kumar Pal, Moumita Patra, Prabhakar K. Pandey, Jitendra K. Bera
Summary: A dicopper (i,i)-NHC complex (1) with pyridine and morpholine-functionalized ligands exhibits both terminal and bridging coordination modes of NHC within the same molecule, and facilitates dual ortho-C-H functionalization of diaryl amines for alkyne hydroarylation. The bimetallic construct of catalyst 1 enables sequential activation of ortho-C-H bonds of two aryl units, leading to diverse 9,10-dihydroacridine derivatives without the need for a directing group.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Antony Sekar Kulandai Raj, Akshay Subhash Narode, Rai-Shung Liu
Summary: This work describes novel gold-catalyzed reactions in which vinyldiazo ketones react with N-(o-alkynylphenyl)imines to yield new indole derivatives, specifically 3-(furan-2-ylmethyl)-1H-indoles, through skeletal rearrangement. The reactions are applicable to a wide range of substrates, and a new mechanism involving the addition of diazo ketones to azomethine ylide intermediates is proposed, resulting in the formation of gold-containing N-alkylated indole intermediates that undergo proton-induced 1,3-group migrations.
Article
Chemistry, Multidisciplinary
Gyeongjin Park, Francois P. Gabbai
Summary: This study focuses on the hydrogen bonding interaction between a metallobasic gold(I) center and an OH functionality, demonstrating the authentic interaction between them. Moreover, experimental results suggest that increasing the acidity of the OH functionality may not necessarily enhance the stability of the Au(I)···H-O interaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Warabhorn Rodphon, Kanokwan Jaithum, Sutida Linkhum, Charnsak Thongsornkleeb, Jumreang Tummatorn, Somsak Ruchirawat
Summary: A cascade oxazole-benzannulation method has been developed for the synthesis of naphtho[2,3-d]oxazoles with a wide variety of substituents. This method offers the advantage of easy accessibility of substrates and the ability to prepare substrates from a variety of commercially available starting materials.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Qingpeng Zhao, Shihao Zhou, Yue Wang, Xiaoyu Yang, Youhui Meng, Yanxin Zhang, Jian Gao
Summary: A one-pot and convergent glycosylation strategy was used to efficiently synthesize a family of 3,6-branched Fuzi alpha-glucans, including the pentasaccharide repeating unit as well as its di- and trimers. The assembly of protected alpha-glucans up to 15-mer exhibited high yields and excellent alpha-stereoselectivity, which was achieved through the synergistic effects of the TolSCl/AgOTf promotion system and the steric beta facial shielding of bulky saccharide residues. The structurally well-defined synthetic alpha-glucans have potential applications in various biological studies.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Organic
Hua Min, Sun Yangxing, Zhang Xueqing, Yao Hui, Huang Nianyu
Summary: A method for the stereoselective synthesis of beta-D-thioglycosides using glucosyl-3-pyridinate donor and thiophenols/thiols catalyzed by Co(BF4)(2) was reported. The reaction has good compatibility with various mercaptans and thiophenols, as well as active sulfur nucleophiles, allowing for the efficient synthesis of thioglycopeptides and providing a new way for the rapid preparation of thioglycosides.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Laurent Cattiaux, Jean-Maurice Mallet
Summary: An alternative method for the synthesis of oligosaccharides based on polyol multi-glycosylation is proposed in this study. The method allows for simple separation based on an increase in molecular mass, without the need for aqueous workup or TLC/detector.
Article
Chemistry, Organic
Jianpeng Chen, Yu Tang, Biao Yu
Summary: A gold(I)-catalyzed rearrangement of glycosyl ortho-allenylbenzoates leading to the formation of C-glycosides has been discovered. The reaction proceeds through the fragmentation of the glycosyl ortho-allylbenzoate into intermediates of glycosyl cation and 3-[phosphine gold(I)methyl]-1H-isochrmen-1-one, followed by their recombination. The allyl gold(I) intermediate has been successfully trapped and characterized.
Article
Chemistry, Multidisciplinary
Xiaofei Shao, Chang Zheng, Peng Xu, Taro Shiraishi, Tomohisa Kuzuyama, Antonio Molinaro, Alba Silipo, Biao Yu
Summary: A collective total synthesis of eight diastereoisomers associated with NMR analysis leads to a full stereochemistry assignment of the structurally unique nucleoside antibiotic A-94964, which features an octuronic acid uridine core decorated with an alpha-D-mannopyranosyl residue and an alpha-D-N-acylglucosaminopyranosyl residue via a phosphodiester bridge.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jie Zhao, Jiazhi Liu, Xinnan Liu, Qi Cao, Hongbo Zhao, Lizhen Liu, Farong Ye, Can Wang, Hong Shao, Dongxiang Xue, Houchao Tao, Bin Li, Biao Yu, Ping Wang
Summary: This article reports a highly efficient method for preparing homogeneous glycosylated IL-2 and reveals that the activity of IL-2 in activating T cell subsets is dependent on glycans, highlighting the possibility of improving current clinical medicine.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xianglai Liu, Yetong Lin, Ao Liu, Qianhui Sun, Huiyong Sun, Peng Xu, Guolong Li, Yingying Song, Weijia Xie, Haopeng Sun, Biao Yu, Wei Li
Summary: The utilization of the DPPA group in glycosylation allowed for efficient synthesis of challenging carbohydrates with excellent beta-selectivities and broad substrate scope. Additionally, the chemoselective removal of the DPPA group under mild Ni(OTf)(2) catalysis facilitated rapid conversion to biologically important molecules.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Yu Tang, Biao Yu
Summary: A mild heteroatom methylation protocol has been developed using the combination of trimethyl phosphate (TMP) and calcium hydroxide (Ca(OH)2), which can be applied under flexible conditions for various O-, N-, and S-nucleophiles.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Dapeng Zhu, Mingyu Geng, Biao Yu
Summary: Starfish have developed a special type of secondary metabolite called starfish saponins to defend against predators and parasites. Among them, starfish cyclic steroid glycosides are structurally unique and pose a significant synthetic challenge.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Xianglai Liu, Yingying Song, Ao Liu, Yueer Zhou, Qian Zhu, Yetong Lin, Huiyong Sun, Kaidi Zhu, Wei Liu, Ning Ding, Weijia Xie, Haopeng Sun, Biao Yu, Peng Xu, Wei Li
Summary: The study demonstrates that PTFAI can serve as a stereodirecting group for 1,2-cis alpha-glycosylation, leading to improved selectivity in glycosylation reactions. The involvement of 6-PTFAI in remote participation was confirmed using low-temperature NMR, shedding light on the reaction mechanism. This strategy shows promise for the synthesis of complex carbohydrates and derivatives.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
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
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, 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, 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)
