Co-reporter: Dr. Jing Zeng;Guangfei Sun;Wang Yao;Yangbin Zhu;Ruobin Wang;Lei Cai;Ke Liu;Qian Zhang; Dr. Xue-Wei Liu; Dr. Qian Wan
Angewandte Chemie International Edition 2017 Volume 56(Issue 19) pp:5227-5231
Publication Date(Web):2017/05/02
DOI:10.1002/anie.201700178
AbstractA concise, diversity-oriented approach for the synthesis of naturally occurring 3-amino- and 3-nitro-2,3,6-trideoxypyranose derivatives and analogues thereof from simple sugars has been developed. In addition, we investigated the synthesis of various 3-aminoglycosyl donors and their application in glycosylation reactions. These studies led to the successful synthesis of a tetrasaccharide containing four different 3-aminosugar components using ortho-alkynylbenzoate donors.
Co-reporter: Dr. Jing Zeng;Guangfei Sun;Wang Yao;Yangbin Zhu;Ruobin Wang;Lei Cai;Ke Liu;Qian Zhang; Dr. Xue-Wei Liu; Dr. Qian Wan
Angewandte Chemie International Edition 2017 Volume 56(Issue 19) pp:5133-5133
Publication Date(Web):2017/05/02
DOI:10.1002/anie.201702798
Tetrasaccharides containing different 3-aminosugar components have been assembled by diversity-oriented synthesis and Yu glycosylation reactions. In their Communication on page 5227 ff., J. Zeng, Q. Wan, and co-workers describe a new type of key intermediate that provides access to naturally occurring 3-aminosugars and analogues thereof. These aminosugars were used in glycosylation reactions and should find applications in drug discovery.
Co-reporter:Jing Zeng;Yang Xu;Hao Wang;Lingkui Meng
Science China Chemistry 2017 Volume 60( Issue 9) pp:1162-1179
Publication Date(Web):19 April 2017
DOI:10.1007/s11426-016-9010-9
2-Deoxy glycosides are widely presented in natural products and clinical reagents. The presence of 2-deoxy glycosides is essential for bioactivities of these compounds. This report provides an overview of the recent advances in the stereoselective synthesis of 2-deoxy glycosides. Particularly, the contents of this review covered the work published since the earlier reviews on this topic by Marzabadi (2000), Lowary (2009), Ding (2012) and Nagorny (2012).
Co-reporter:Yang Xu, Qian Zhang, Ying Xiao, Pinru Wu, Wei Chen, Zejin Song, Xiong Xiao, Lingkui Meng, Jing Zeng, Qian Wan
Tetrahedron Letters 2017 Volume 58, Issue 24(Issue 24) pp:
Publication Date(Web):14 June 2017
DOI:10.1016/j.tetlet.2017.05.014
•Two practical synthetic methods to disarmed SPTB glycosides are reported.•Both methods can make SPTB glycosides in gram scale.•Affords an easy access to various disarmed SPTB glycosides in high yields.Practical synthetic methods to latent disarmed S-2-(2-propylthio)benzyl (SPTB) glycosides for interrupted Pummerer reaction mediated glycosylation have been discovered. Among them, both coupling reaction of PTB-Cl with glycosyl thiols and BF3·OEt2 promoted reaction of peracylated glycosides with PTB-SH produced peracylated SPTB glycosides in large scales and with high efficiency.Download high-res image (101KB)Download full-size image
Co-reporter:Wei Chen, Jing Zeng, Hao Wang, Xiong Xiao, Lingkui Meng, Qian Wan
Carbohydrate Research 2017 Volume 452(Volume 452) pp:
Publication Date(Web):27 November 2017
DOI:10.1016/j.carres.2017.09.013
•18O isotopic labeling reaction was carried out to track the leaving group.•An unreactive cyclic oxo-sulfonium ion intermediate was formed from the leaving group upon activation.•This intermediate was hydrolyzed to PSB-OH in the aqueous work-up process.•The hydrolysis pathway was clarified by 18O isotopic labeling reaction.In our recently developed interrupted Pummerer reaction mediated glycosylation with O-2-[(propan-2-yl)sulfinyl]benzyl (OPSB) glycosides as glycosyl donors, the anomeric leaving group was recovered as a benzyl alcohol which didn't affect the glycosylation efficiency. To investigate the mechanism of the occurrence of this alcohol, an 18O isotopic labeling reaction was carried out to track the leaving group. It was found that the benzyl alcohol was generated during the aqueous work up process from an inactive cyclic oxo-sulfonium ion intermediate. It was also proved that H2O prefer to attack the sulfur atom position during the hydrolysis of the intermediate.Download high-res image (101KB)Download full-size image
Co-reporter:Jing Zeng;Guangfei Sun;Ruobin Wang;Shuxin Zhang;Shuang Teng;Zhiwen Liao;Lingkui Meng
Organic Chemistry Frontiers 2017 vol. 4(Issue 12) pp:2450-2454
Publication Date(Web):2017/11/21
DOI:10.1039/C7QO00648A
A diversified synthesis of 3-aminosugar analogues of digitoxin and digoxin with potent anticancer activities was explored. The synthesis was based on a highly efficient gold-catalyzed glycosylation reaction with alkynylbenzoate 3-aminoglycosides as glycosyl donors. According to this strategy, a small library containing digitoxin and digoxin analogues with various 3-aminosugar scaffolds was successfully constructed.
Co-reporter:Xiong Xiao, Yueqi Zhao, Penghua Shu, Xiang Zhao, Yan Liu, Jiuchang Sun, Qian Zhang, Jing Zeng, and Qian Wan
Journal of the American Chemical Society 2016 Volume 138(Issue 40) pp:13402-13407
Publication Date(Web):September 12, 2016
DOI:10.1021/jacs.6b08305
S-glycosides, S-2-(2-propylthio)benzyl (SPTB) glycosides, were converted to the corresponding oxidized glycosyl donors, S-2-(2-propylsulfinyl)benzyl (SPSB) glycosides, by simple and selective oxidation. Treatment of disarmed SPSB donor and various acceptors with triflic anhydride provided the desired glycosides in good to excellent yields. Meanwhile, observation of thiosulfinate, thiosulfonate, and disulfide suggested that the leaving group was activated via an interrupted Pummerer reaction. The disarmed SPSB thioglycosyl donors could be selectively activated in the presence of various thioglycosides with remote activation mode. Finally, two natural hepatoprotective glycosides, Leonoside E and Leonuriside B, were efficiently synthesized in a convergent manner with this newly developed method.
Co-reporter:Penghua Shu, Jing Zeng, Jinyi Tao, Yueqi Zhao, Guangmin Yao and Qian Wan
Green Chemistry 2015 vol. 17(Issue 4) pp:2545-2551
Publication Date(Web):16 Feb 2015
DOI:10.1039/C5GC00084J
Glycosyl thiols are useful building blocks for the construction of compounds of biological and synthetic importance. Herein, we report a practical synthetic approach toward the efficient synthesis of glycosyl thiols via chemo- and regioselective S-deacetylation inspired by native chemical ligation. This strategy allows the large scale synthesis of glycosyl thiols by simple purification steps without column chromatography. In addition, deacetylation reagents (DTT) could also be recovered and regenerated by a simple process. Thiol containing taxol and artemisinin analogues were successfully prepared based on this methodology. Finally, auranofin, a glucose-based oral drug used to treat rheumatoid arthritis, was synthesized in concise steps and overall high yields.
Co-reporter:Penghua Shu;Xiong Xiao;Yueqi Zhao;Yang Xu;Wang Yao;Jinyi Tao;Hao Wang;Dr. Guangmin Yao;Dr. Zimin Lu;Dr. Jing Zeng;Dr. Qian Wan
Angewandte Chemie 2015 Volume 127( Issue 48) pp:14640-14644
Publication Date(Web):
DOI:10.1002/ange.201507861
Abstract
Latent O-glycosides, 2-(2-propylthiol)benzyl (PTB) glycosides, were converted into the corresponding active glycosyl donors, 2-(2-propylsulfinyl)benzyl (PSB) glycosides, by a simple and efficient oxidation. Treatment of the PSB donor and various acceptors with triflic anhydride provided the desired glycosides in good to excellent yields. The leaving group, which was activated by an interrupted Pummerer reaction, can be recycled (PSB-OH) and regenerated as the precursor (PTB-OH). A natural hepatoprotective glycoside, leonoside F, was efficiently synthesized in a convergent [3+1] manner with this newly developed method. The present total synthesis also led to a structural revision of this phenylethanoid glycoside.
Co-reporter:Penghua Shu;Xiong Xiao;Yueqi Zhao;Yang Xu;Wang Yao;Jinyi Tao;Hao Wang;Dr. Guangmin Yao;Dr. Zimin Lu;Dr. Jing Zeng;Dr. Qian Wan
Angewandte Chemie International Edition 2015 Volume 54( Issue 48) pp:14432-14436
Publication Date(Web):
DOI:10.1002/anie.201507861
Abstract
Latent O-glycosides, 2-(2-propylthiol)benzyl (PTB) glycosides, were converted into the corresponding active glycosyl donors, 2-(2-propylsulfinyl)benzyl (PSB) glycosides, by a simple and efficient oxidation. Treatment of the PSB donor and various acceptors with triflic anhydride provided the desired glycosides in good to excellent yields. The leaving group, which was activated by an interrupted Pummerer reaction, can be recycled (PSB-OH) and regenerated as the precursor (PTB-OH). A natural hepatoprotective glycoside, leonoside F, was efficiently synthesized in a convergent [3+1] manner with this newly developed method. The present total synthesis also led to a structural revision of this phenylethanoid glycoside.
Co-reporter:Ke Yang, Si-Zhe Li, Yin-Hu Wang, Wen-Zhen Zhang, Zhan-Hui Xu, Xiang-Yong Zhou, Rong-Xiu Zhu, Jun Luo and Qian Wan
RSC Advances 2014 vol. 4(Issue 13) pp:6517-6526
Publication Date(Web):09 Jan 2014
DOI:10.1039/C3RA46723F
A comparative study was conducted to evaluate the chiral recognition ability of several inherently chiral calixcrown carboxylic acids towards chiral aminoalcohols. 1H NMR titration experiments indicated that inherently chiral calixcrown carboxylic acids each having a phenolic hydroxyl group possess superior chiral recognition ability to the completely alkylated calixarene derivatives. Particularly, inherently chiral calix[4]crown-6 carboxylic acid cone conformer 10 demonstrated significant enantioselectivity in its chiral recognition towards 2-amino-3-methyl-1-butanol (G3) and 2-amino-2-phenylethanol (G6), with the (cS)-10 preferably binding the (S)-guests. Job plots confirmed that 10 and both enantiomers of G3/G6 form 1:1 instantaneous complexes. DFT calculations revealed the existence of multiple hydrogen bonds in the host–guest complexes. The enantioselectivity of the recognition is ascribed to the stronger hydrogen bonding between (cS)-10 and (S)-guests than between (cS)-10 and (R)-guests, based on the calculation results.
Co-reporter:Hao Wang;Jinyi Tao;Xinpei Cai;Wei Chen;Yueqi Zhao;Yang Xu;Wang Yao;Dr. Jing Zeng;Dr. Qian Wan
Chemistry - A European Journal 2014 Volume 20( Issue 52) pp:17319-17323
Publication Date(Web):
DOI:10.1002/chem.201405516
Abstract
2-Deoxy sugars and their derivatives occur abundantly in many pharmaceutically important natural products. However, the construction of specific 2-deoxy-glycosidic bonds remains as a challenge. Herein, we report an efficient way to prepare 2-deoxy-α-glycosides by glycosylation of 2-iodo-glycosyl acetate and subsequent visible-light-mediated tin-free reductive deiodination. We have successfully applied the postglycosylational-deiodination strategy in the synthesis of more than 30 mono-, di-, tri-, tetra- and pentadeoxysaccharides with excellent stereoselectivity and efficiency. This method has also been applied to the synthesis of a 2-deoxy-tetrasaccharide containing four α-linkages.
Co-reporter:Si-Zhe Li, Ke Yang, Hong-Bing Liu, Yu-Xiang Xia, Rong-Xiu Zhu, Jun Luo, Qian Wan
Tetrahedron Letters 2013 Volume 54(Issue 44) pp:5901-5906
Publication Date(Web):30 October 2013
DOI:10.1016/j.tetlet.2013.08.091
Inherently chiral biscalixarenes with hetero-cavities were synthesized by a covalent assembly of p-tert-butylcalix[5]arene with a 1,3-substituted calix[4]arene via 1,3-alkylation reaction and subsequent desymmetrization. The racemates were resolved by chiral HPLC method. 1H NMR spectra, VT-NMR spectra, and theoretical calculations support that the calix[5]arene subunit of the inherently chiral calix[4][5]arene ester adopts a cone-in conformation, with the aromatic ring bearing the CH2CO2Et group tilting inward the calix[5]arene cavity. By contrast, such a cone-in structural feature of the calix[5]arene subunit disappears for the corresponding inherently chiral calix[4][5]arene carboxylic acid, due to the intramolecular hydrogen bonding between the carboxyl group and an ethereal oxygen of the glycolic chain.
Co-reporter:Penghua Shu, Wang Yao, Xiong Xiao, Jiuchang Sun, Xiang Zhao, Yueqi Zhao, Yang Xu, Jinyi Tao, Guangmin Yao, Jing Zeng and Qian Wan
Inorganic Chemistry Frontiers 2016 - vol. 3(Issue 2) pp:NaN183-183
Publication Date(Web):2015/12/14
DOI:10.1039/C5QO00359H
2-(2-Propylsulfinyl)benzyl glycoside was designed as a new type of glycosyl donor which could be activated via remote mode. This glycosyl donor and its reduced form could act as active and latent donors respectively in a latent-active glycosylation strategy. Details of the discovery of this novel glycosyl donor are reported in this article.
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