Orthogonal photoswitching of heterobivalent azobenzene glycoclusters: the effect of glycoligand orientation in bacterial adhesion

• Leon M. Friedrich and
• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2025, 21, 736–748, doi:10.3762/bjoc.21.57

• thiomannopyranoside 10 yielded the protected glycocluster 12 in 60% yield. A subsequent Zemplén deacetylation gave the homobivalent glycocluster 6αMan3αMan 2 in quantitative yield (Scheme 1). In order to synthesize the glycoazobenzene antennas contained in the glycoclusters 1 and 2, the β-ᴅ-glucopyranosyloxy- and the

• -dithio-ᴅ-threitol) [36] (Scheme 2A). The crude thiol 14 was subsequently subjected to a Buchwald–Hartwig–Migita cross-coupling reaction with the literature-known azobenzene thioglucoside 15 [37], resulting in the (6-thioglucosyl)mannoside 16 in 63% yield over two steps. Zemplén deacetylation [38] gave

• antenna 17 in 73% over two steps. Subsequent deacetylation quantitatively yielded 6αMan 4 (Scheme 2A). Finally, the third required glycoazobenzene antenna, the 3-(α-ᴅ-mannopyranosyl)mannoside 3αMan 5, was directly obtained from the known mannosyloxyazobenzene mannoside 18 [24] after Zemplén deprotection

Cyclodextrin-based rotaxanes for polymer materials: challenge on simultaneous realization of inexpensive production and defined structures

• Yosuke Akae

Beilstein J. Org. Chem. 2024, 20, 3026–3049, doi:10.3762/bjoc.20.252

N-Glycosides of indigo, indirubin, and isoindigo: blue, red, and yellow sugars and their cancerostatic activity

• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 2840–2869, doi:10.3762/bjoc.20.240

• -mannose (14) afforded indigo-N-mannoside α-15a, albeit, in low yield (Scheme 11) [21]. Deacetylation afforded product α-15b. Indirubin-N-glycosides (red sugars) In contrast to indigo, indirubin is a non-symmetrical compound containing an amine- and an amide-type nitrogen atom. In our group, we developed a

• (Scheme 13) failed for the reaction of β-29a and β-29b with isatin. Likewise, various other conditions for base- or acid-mediated deacetylation and aldol-type condensation, typically used for the synthesis of non-glycosylated indirubins, proved to be unsuccessful. However, the acetyl group of β-29a could

• which was successfully deprotected to give the desired product β-72a. It is worth to be noted that isatin-N-rhamnoside β-70a is not available by cyclization of the corresponding benzyl-protected aniline-N-rhamnoside with oxalyl chloride or by deacetylation of β-16a and subsequent benzylation

Computational toolbox for the analysis of protein–glycan interactions

• Ferran Nieto-Fabregat,
• Maria Pia Lenza,
• Angela Marseglia,
• Cristina Di Carluccio,
• Antonio Molinaro,
• Alba Silipo and
• Roberta Marchetti

Beilstein J. Org. Chem. 2024, 20, 2084–2107, doi:10.3762/bjoc.20.180

The Groebke–Blackburn–Bienaymé reaction in its maturity: innovation and improvements since its 21st birthday (2019–2023)

• Cristina Martini,
• Muhammad Idham Darussalam Mardjan and
• Andrea Basso

Beilstein J. Org. Chem. 2024, 20, 1839–1879, doi:10.3762/bjoc.20.162

• yield of 83–95%. The second strategy, based on the deacetylation of 29 followed by the GBB-3CR, led to a lower overall yield of 21–23%. The reaction with different 2-aminopyridines and alkyl/aryl isocyanides afforded the intermediates 30 in 86 to 96% yield, and the subsequent deacetylation with

• potassium carbonate was almost quantitative (97–99% yield). It is worth mentioning that the GBB reaction starting from the deacetylated substrate also leads to good results (83–91% of yield), but the overall yield is lowered due to a sluggish deacetylation reaction of 29. Sugar-based aldehydes were employed

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

• concentrated under reduced pressure and purified by flash chromatography (cyclohexane/EtOAc 7:3) to give the thioglycoside. General procedure IV for the Zemplén deacetylation: To a seal tube containing the galactose derivatives in dry MeOH (0.15 M), NaOMe (30 mol %, 0.5 M sol. in MeOH) was added. The mixture

Synthesis of the 3’-O-sulfated TF antigen with a TEG-N₃ linker for glycodendrimersomes preparation to study lectin binding

• Mark Reihill,
• Hanyue Ma,
• Dennis Bengtsson and
• Stefan Oscarson

Beilstein J. Org. Chem. 2024, 20, 173–180, doi:10.3762/bjoc.20.17

• large excess of HF·Py (40 equiv) proved to be necessary to remove the bulky silyl group. After concentration, the crude product was acetylated (Ac2O/Py, 1:2, v/v), furnishing per-acetylated compound 8 in a 53% yield over the 3 steps. Deacetylation of 8 with freshly prepared 1 M NaOMe/MeOH in MeOH at pH

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

pH-Responsive fluorescent supramolecular nanoparticles based on tetraphenylethylene-labelled chitosan and a six-fold carboxylated tribenzotriquinacene

• Nan Yang,
• Yi-Yan Zhu,
• Wei-Xiu Lin,
• Yi-Long Lu and
• Wen-Rong Xu

Beilstein J. Org. Chem. 2023, 19, 635–645, doi:10.3762/bjoc.19.45

• of deacetylation greater than 95% (viscosity 100, 200 mPa·s) was purchased from Aladdin. All other reagents and solvents were purchased from Xilong Science as analytical grade and were used without further purification. TBTQ-C6 and TPE-CHO were synthesized and purified according to the previously

Combretastatins D series and analogues: from isolation, synthetic challenges and biological activities

• Jorge de Lima Neto and
• Paulo Henrique Menezes

Beilstein J. Org. Chem. 2023, 19, 399–427, doi:10.3762/bjoc.19.31

• (129) followed by the reduction [61] of the aldehyde gave the corresponding benzyl alcohol 131 in 76% yield. Deacetylation in the presence of hydrazine [62] followed by intramolecular thioetherification led to the macrocycle 133. Finally, the oxidation of the obtained thioether to the corresponding

• to both, cleavage of the Piv group and reduction of the aldehyde yielding the diol 147. Selective oxidation [67] of the benzyl alcohol with MnO2 gave the compound 148, which was esterified with S-acetylthioacetic acid (129) and reduced to the benzyl alcohol 150. Deacetylation followed by

Preparation of β-cyclodextrin/polysaccharide foams using saponin

• Max Petitjean and
• José Ramón Isasi

Beilstein J. Org. Chem. 2023, 19, 78–88, doi:10.3762/bjoc.19.7

• , though their macroporosities are remarkably different. Experimental Materials β-cyclodextrin (Wacker, 12.5% H2O), xanthan gum (Sigma-Aldrich), locust bean gum (Sigma-Aldrich), chitosan (deacetylation degree of 90%), citric acid (Panreac AppliChem) and dibasic sodium phosphate (Na2HPO4 ≥ 98%), soapbark

Preparation of β-cyclodextrin-based dimers with selectively methylated rims and their use for solubilization of tetracene

• Konstantin Lebedinskiy,
• Volodymyr Lobaz and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2022, 18, 1596–1606, doi:10.3762/bjoc.18.170

• deacetylation of 8, proved to be not reactive enough to complete the reaction in 24 h under the conditions used to prepare the dimer 5. The prolongation of the reaction time increased the yield slightly, but it was still too low (17%). To improve the yield, we used lithium iodide and increased the temperature

Synthesis of C6-modified mannose 1-phosphates and evaluation of derived sugar nucleotides against GDP-mannose dehydrogenase

• Sanaz Ahmadipour,
• Alice J. C. Wahart,
• Jonathan P. Dolan,
• Laura Beswick,
• Chris S. Hawes,
• Robert A. Field and
• Gavin J. Miller

Beilstein J. Org. Chem. 2022, 18, 1379–1384, doi:10.3762/bjoc.18.142

• completed a selective anomeric deacetylation on a gram-scale using ammonium acetate in DMF, to afford hemi-acetal 15 in good yield (80%) [11]. This was followed by phosphorylation of the anomeric position using diphenylphosphoryl chloride as the phosphorous electrophile, following deprotonation of 15 using

Polymer and small molecule mechanochemistry: closer than ever

• José G. Hernández

Beilstein J. Org. Chem. 2022, 18, 1225–1235, doi:10.3762/bjoc.18.128

• ball mill (Figure 1c) enhances the depolymerization of acid-impregnated chitin more selectively towards glycosidic bond cleavage (i.e., backbone rupture) over amide bond breakage (i.e., deacetylation) [38][45]. Notably, the result is different for the reaction in solution, where scission of both bonds

• as the model compound showed that the application of pulling forces to selected atoms in the dimer perturb the reaction, making the depolymerization easier to occur [45]. In contrast, no change in the activation energy of the deacetylation step was observed with the introduction of the pulling forces

Synthesis and HDAC inhibitory activity of pyrimidine-based hydroxamic acids

• Virginija Jakubkiene,
• Gabrielius Ernis Valiulis,
• Markus Schweipert,
• Asta Zubriene,
• Daumantas Matulis,
• Franz-Josef Meyer-Almes and
• Sigitas Tumkevicius

Beilstein J. Org. Chem. 2022, 18, 837–844, doi:10.3762/bjoc.18.84

• (HDACs) play an essential role in the transcriptional regulation of cells through the deacetylation of nuclear histone and non-histone proteins and are promising therapeutic targets for the treatment of various diseases. Here, the synthesis of new compounds in which a hydroxamic acid residue is attached

Synthesis and late stage modifications of Cyl derivatives

• Phil Servatius and
• Uli Kazmaier

Beilstein J. Org. Chem. 2022, 18, 174–181, doi:10.3762/bjoc.18.19

• B (Figure 1) is a cyclic tetrapeptide with a rather unusual epoxyketone side chain and was found to be a strong inhibitor of histone deacetylases (HDACs) [4][5]. HDACs are nuclear isozymes that regulate gene transcription via a dynamic process of acetylation and deacetylation of lysine residues of

Chemical and chemoenzymatic routes to bridged homoarabinofuranosylpyrimidines: Bicyclic AZT analogues

• Sandeep Kumar,
• Jyotirmoy Maity,
• Banty Kumar,
• Sumit Kumar and
• Ashok K. Prasad

Beilstein J. Org. Chem. 2022, 18, 95–101, doi:10.3762/bjoc.18.10

• (trimethylsilyl)acetamide (BSA) and trimethylsilyl trifluoromethanesulfonate (TMSOTf) afforded nucleosides 13a,b. Further, deacetylation of the triacetylated azidoallofuranosyl nucleosides 13a,b with K2CO3 in methanol/water led to the formation of 3′-azido-3′-deoxy-β-ᴅ-allofuranosyl nucleosides 14a,b in 85

• anomeric triacetylated sugars 19a,b with thymine and uracil in the presence of BSA and TMSOTf in acetonitrile afforded nucleosides 20a,b, respectively in high yields. The deacetylation of these nucleosides was carried out using K2CO3 in a solvent mixture of methanol and water (9:1) to afford nucleoside 21a

Total synthesis of the O-antigen repeating unit of Providencia stuartii O49 serotype through linear and one-pot assemblies

• Tanmoy Halder and
• Somnath Yadav

Beilstein J. Org. Chem. 2021, 17, 2915–2921, doi:10.3762/bjoc.17.199

• on the hydroxy groups. First, the concomitant removal of the Troc group and the N-acetylation was achieved using Zn/AcOH/Ac2O 3:2:1 as reagent in one pot (Scheme 6) [52]. Then, O-deacetylation was accomplished by using a catalytic amount of NaOMe in MeOH at room temperature. Finally, the benzylidene

Synthetic strategies toward 1,3-oxathiolane nucleoside analogues

• Umesh P. Aher,
• Dhananjai Srivastava,
• Girij P. Singh and
• Jayashree B. S

Beilstein J. Org. Chem. 2021, 17, 2680–2715, doi:10.3762/bjoc.17.182

• the α-anomer were produced individually by further deacetylation using methanolic ammonia and desilylation with TBAF [33]. (+)-BCH-189 (1a) was found to be less active against HIV-1 (EC50 = 0.2 µM in CEM cells) than (−)-BCH-189 (1, EC50 = 0.07 µM in CEM cells) [14]. Chu and co-workers [44] reported a

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

Synthesis of multiply fluorinated N-acetyl-D-glucosamine and D-galactosamine analogs via the corresponding deoxyfluorinated glucosazide and galactosazide phenyl thioglycosides

• Vojtěch Hamala,
• Lucie Červenková Šťastná,
• Martin Kurfiřt,
• Petra Cuřínová,
• Martin Dračínský and
• Jindřich Karban

Beilstein J. Org. Chem. 2021, 17, 1086–1095, doi:10.3762/bjoc.17.85

• . Deoxyfluorination at C6 should then afford intermediates 6. Protecting-group manipulation of intermediates 4 and 6 should deliver the required fluoro analogs. The initially contemplated conversion of intermediates 3 into acetates 5 [26], followed by base-catalyzed O-deacetylation, led to substantial decomposition

Stereoselective syntheses of 3-aminocyclooctanetriols and halocyclooctanetriols

• Emine Salamci and
• Yunus Zozik

Beilstein J. Org. Chem. 2021, 17, 705–710, doi:10.3762/bjoc.17.59

• . Similarly, the configuration of the chlorine atom and the acetoxy groups in 26 was determined with 1H NMR and COSY spectra. Finally, deacetylation of chlorotriacetates 25 and 26 was carried out with HCl(g) in MeOH to give the free chlorotriols derivatives 23 and 24. Conclusion The synthesis of two

Synthesis of (Z)-3-[amino(phenyl)methylidene]-1,3-dihydro-2H-indol-2-ones using an Eschenmoser coupling reaction

• Lukáš Marek,
• Lukáš Kolman,
• Jiří Váňa,
• Jan Svoboda and
• Jiří Hanusek

Beilstein J. Org. Chem. 2021, 17, 527–539, doi:10.3762/bjoc.17.47

• derivative. Such nitrogen protection/deprotection (e.g., acetylation/deacetylation) is often used in the other synthetic strategies described in Scheme 1. Therefore, the starting isatin was acetylated first with acetic anhydride [47] in 95% yield and then reduced with various complex borohydrides (e.g

Regioselective chemoenzymatic syntheses of ferulate conjugates as chromogenic substrates for feruloyl esterases

• Olga Gherbovet,
• Fernando Ferreira,
• Apolline Clément,
• Mélanie Ragon,
• Julien Durand,
• Sophie Bozonnet,
• Michael J. O'Donohue and
• Régis Fauré

Beilstein J. Org. Chem. 2021, 17, 325–333, doi:10.3762/bjoc.17.30

• the primary hydroxy group compare favorably with the previously reported overall yield (46 and 47%, respectively, in three steps) [15][16][17][29], which relate to the selective enzymatic O-5-deacetylation and esterification of the primary hydroxy group and a final deprotection of the 2,3-O-acetyl

The preparation and properties of 1,1-difluorocyclopropane derivatives

• Kymbat S. Adekenova,
• Peter B. Wyatt and
• Sergazy M. Adekenov

Beilstein J. Org. Chem. 2021, 17, 245–272, doi:10.3762/bjoc.17.25

• targets of biological interest was provided by Csuk and Eversmann [32] who performed the synthesis of difluorinated nucleosides (Scheme 11). The difluorocyclopropane derivative 14 was prepared using sodium chlorodifluoroacetate (12) as a source of the carbene (Scheme 11). The subsequent deacetylation of

• [81]. The authors obtained the chiral monoacetate intermediates (R)-78 and (S)-80 by lipase-catalyzed methods. The lipase-catalyzed asymmetric transesterification of prochiral diol 77 and the deacetylation of the prochiral diacetate 79 resulted in the formation of the (R)-monoacetate (R)-78 and (S

• )-monoacetate (S)-80, respectively (Scheme 32). As for the transesterification, a high yield (96.5%) and enantioselectivity (91.3% ee) were obtained using lipase PS in benzene. In the case of the deacetylation, the use of Amano PS lipase in acetone gave a high yield (86.2%), enantioselectivity (91.7% ee), and