Structural analysis of stereoselective galactose pyruvylation toward the synthesis of bacterial capsular polysaccharides

• Tsun-Yi Chiang,
• Mei-Huei Lin,
• Chun-Wei Chang,
• Jinq-Chyi Lee and
• Cheng-Chung Wang

Beilstein J. Org. Chem. 2025, 21, 1671–1677, doi:10.3762/bjoc.21.131

• same reaction mixture, in situ activation of disaccharide donor 8 and acceptor 9 using TolSCl/AgOTf reagent combination was introduced. This two-step, one-pot glycosylation gave a 42% yield of disaccharide 10, maintaining good β-stereoselectivity at the galactosyl linkage (α/β = 1:5.8). The 2

• pyruvate ketals. The modified galactose moiety was then used for the synthesis of the trisaccharide PS A1 precursor via a one-pot glycosylation strategy, where the glycosylation product was efficiently formed based on differences in acceptor reactivity. The synthetic protocol was concise, yielding

Chemical synthesis of glycan motifs from the antitumor agent PI-88 through an orthogonal one-pot glycosylation strategy

• Shaokang Yang,
• Xingchun Sun,
• Hanyingzi Fan and
• Guozhi Xiao

Beilstein J. Org. Chem. 2025, 21, 1587–1594, doi:10.3762/bjoc.21.122

• Academy of Sciences, Kunming 650201, China 10.3762/bjoc.21.122 Abstract Chemical synthesis of monophosphorylated glycan motifs from the antitumor agent PI-88 has been achieved through an orthogonal one-pot glycosylation strategy on the basis of glycosyl ortho-(1-phenylvinyl)benzoates, which not only

• )benzoates; one-pot glycosylation; PI-88; Introduction Carbohydrates as one of four essential biomolecules have been widely recognized as important targets for the development of carbohydrate-based therapeutics [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. The example in point is the

• waste [37][38][39][40][41][42]. Recently, we introduced a new one-pot glycosylation strategy on the basis of recently developed glycosyl ortho-(1-phenylvinyl)benzoate (PVB) [43][44][45] donors from our group, which has been successfully applied to the streamline synthesis of various glycans from

The effect of neighbouring group participation and possible long range remote group participation in O-glycosylation

• Rituparna Das and
• Balaram Mukhopadhyay

Beilstein J. Org. Chem. 2025, 21, 369–406, doi:10.3762/bjoc.21.27

• rigorous planning of one-pot glycosylation the role of a neighbouring group and possible effect of remote participating groups comes into play. One-pot glycosylations have also opened the door of the automated oligosaccharide synthesis which applies the principle of solid-phase synthesis [59][60][61][62

Photoswitchable glycoligands targeting Pseudomonas aeruginosa LecA

• Yu Fan,
• Ahmed El Rhaz,
• Stéphane Maisonneuve,
• Emilie Gillon,
• Maha Fatthalla,
• Franck Le Bideau,
• Guillaume Laurent,
• Samir Messaoudi,
• Anne Imberty and
• Juan Xie

Beilstein J. Org. Chem. 2024, 20, 1486–1496, doi:10.3762/bjoc.20.132

• commercially available p,p’-dihydroxyazobenzene (6), by using our recently developed DMC (2-chloro-1,3-dimethylimidazolinium chloride)-mediated one-pot glycosylation method in water [28], followed by O-alkylation of the remaining hydroxy group with BrCH2CH2NHBoc and acidic deprotection (Scheme 1). Three

Optimizations of lipid II synthesis: an essential glycolipid precursor in bacterial cell wall synthesis and a validated antibiotic target

• Milandip Karak,
• Cian R. Cloonan,
• Brad R. Baker,
• Rachel V. K. Cochrane and
• Stephen A. Cochrane

Beilstein J. Org. Chem. 2024, 20, 220–227, doi:10.3762/bjoc.20.22

• disaccharide synthesis alongside C6-protected acceptors (2a or 2b in Figure 2) [10][11][14][15][37][38]. More recently, an innovative one-pot glycosylation approach using a (2,6-dichloro-4-methoxyphenyl)(2,4-dichlorophenyl)-protected glycosyl acceptor has been developed, demonstrating satisfactory stability

Progress and challenges in the synthesis of sequence controlled polysaccharides

• Giulio Fittolani,
• Theodore Tyrikos-Ergas,
• Denisa Vargová,
• Manishkumar A. Chaube and
• Martina Delbianco

Beilstein J. Org. Chem. 2021, 17, 1981–2025, doi:10.3762/bjoc.17.129

• (6mer, 8mer, 10mer and 12mer) following a convergent preactivation-based iterative strategy [135]. These compounds were subsequently conjugated to keyhole limpet hemocyanin, revealing that the length of the glucans affected the immunogenic properties. A pre-activation-based iterative one-pot

• glycosylation method was also employed to access different branched structures having β(1–3)- and β(1–6)-linked Glc appendances on a β(1–3) backbone [136]. To date, the longer β(1–3)-glucans [137][138] were obtained using a 2-O-acylated donor, to ensure β-selectivity, followed by deacylation and use of the

Synthesis of the tetrasaccharide repeating unit of the O-specific polysaccharide of Azospirillum doebereinerae type strain GSF71^T using linear and one-pot iterative glycosylations

• Arin Gucchait,
• Pradip Shit and
• Anup Kumar Misra

Beilstein J. Org. Chem. 2020, 16, 1700–1705, doi:10.3762/bjoc.16.141

• min; (d) acetic anhydride, pyridine, CH2Cl2, 0 °C, 5 h; (e) Et3SiH, 20% Pd(OH)2/C, CH3OH, rt, 24 h, 50% overall yield for three steps. Iterative stereoselective three-step one-pot glycosylation. Reaction conditions: (a) NIS, HClO4-SiO2, CH2Cl2, MS 4 Å, –15 °C, 30 min, then 20 °C, 30 min. Supporting

Glycosylation reactions mediated by hypervalent iodine: application to the synthesis of nucleosides and carbohydrates

• Yuichi Yoshimura,
• Hideaki Wakamatsu,
• Yoshihiro Natori,
• Yukako Saito and
• Noriaki Minakawa

Beilstein J. Org. Chem. 2018, 14, 1595–1618, doi:10.3762/bjoc.14.137

• latter reaction was employed to synthesize dihydropyranonucleosides. Oxidative scission is a characteristic reaction mediated by hypervalent iodine reagents and is typically used for dehomologation of sugars. A one-pot glycosylation using this reaction was also developed for the synthesis of acyclic

Synthetic avenues towards a tetrasaccharide related to Streptococcus pneumonia of serotype 6A

• Aritra Chaudhury,
• Mana Mohan Mukherjee and
• Rina Ghosh

Beilstein J. Org. Chem. 2018, 14, 1095–1102, doi:10.3762/bjoc.14.95

• oligosaccharide synthesis. We have synthesized the aforesaid tetrasaccharide (SPn 6A) based on both stepwise and sequential one-pot glycosylation reactions using easily accessible common building blocks; eventually similar overall yields were obtained in both cases. Keywords: carbohydrates; glycosylation

Preactivation-based chemoselective glycosylations: A powerful strategy for oligosaccharide assembly

• Weizhun Yang,
• Bo Yang,
• Sherif Ramadan and
• Xuefei Huang

Beilstein J. Org. Chem. 2017, 13, 2094–2114, doi:10.3762/bjoc.13.207

• nucleophilic side products following donor activation. Through extensive experimentation, Huang, Ye and co-workers successfully developed an iterative one-pot glycosylation strategy using the p-TolSCl/AgOTf promoter system and p-tolyl thioglycosides as building blocks [18]. A possible mechanism for this

• monosaccharide building blocks (106–108) led to the formation of hexasaccharide 109 in an excellent 63% yield in one pot on a gram scale (Scheme 19a). This is the largest number of glycosylation reactions that have been performed in one pot to date. Further iterative five-component one-pot glycosylation (111

• synthesis of libraries of oligosaccharides by divergently combining building blocks. An example of this is the preparation of a library of heparan sulfate oligosaccharides (Figure 8) [74]. Alternating use of disaccharide building blocks 127 and 128 in preactivation-based one-pot glycosylation led to a panel

Strategies toward protecting group-free glycosylation through selective activation of the anomeric center

• A. Michael Downey and
• Michal Hocek

Beilstein J. Org. Chem. 2017, 13, 1239–1279, doi:10.3762/bjoc.13.123

Silyl-protective groups influencing the reactivity and selectivity in glycosylations

• Mikael Bols and
• Christian Marcus Pedersen

Beilstein J. Org. Chem. 2017, 13, 93–105, doi:10.3762/bjoc.13.12

• than the corresponding benzylated thioglycosides in competition reactions and used the reactivity differences in a one-pot glycosylation reaction between 37, a disarmed donor/acceptor 38 and an acceptor 39, which gave the trisaccharide 40 in a remarkable yield of 88% (Scheme 7). This reaction works so

Efficient routes toward the synthesis of the D-rhamno-trisaccharide related to the A-band polysaccharide of Pseudomonas aeruginosa

• Aritra Chaudhury,
• Sajal K. Maity and
• Rina Ghosh

Beilstein J. Org. Chem. 2014, 10, 1488–1494, doi:10.3762/bjoc.10.153

• allowed efficient access to the trisaccharide target via stepwise glycosylation as well as a one-pot glycosylation protocol. In a different approach, a 4,6-O-benzylidene D-manno-trisaccharide derivative was synthesized, which upon global 6-O-deoxygenation followed by deprotection generated the target D

• ; reagents and conditions: i) TMSOTf, DCM, molecular sieves 4 Å, N2, −50 °C; ii) NIS, TMSOTf, DCM, molecular sieves 4 Å, N2, −10 °C; iii) NaOMe, MeOH, rt, 12 h. Synthesis of the trisaccharide by sequential one-pot glycosylation reactions; reagents and conditions: i) (a) TMSOTf, DCM, molecular sieves 4 Å, N2

Straightforward synthesis of a tetrasaccharide repeating unit corresponding to the O-antigen of Escherichia coli O16

• Manas Jana and
• Anup Kumar Misra

Beilstein J. Org. Chem. 2013, 9, 1757–1762, doi:10.3762/bjoc.9.203

• achieved following a sequential glycosylation strategy. A minimum number of steps was used for the synthesis of the target compound involving a one-pot glycosylation and a protecting group manipulation. All intermediate reactions afford their products in high yield, and the glycosylation steps are

• iodonium ion mediated glycosylation conditions; (c) the use of p-methoxybenzyl (PMB) ether protection as an in situ removable protecting group in a one-pot glycosylation reaction and its removal [17] and (d) the use of galactofuranosidic thioglycoside as a glycosyl donor. The iodonium ion promoted