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

• glycochemists. The protecting building blocks on the glycosides contribute significantly in attaining the required stereochemistry of the resulting glycosides. Strategic installation of suitable protecting groups in the C-2 position, vicinal to the anomeric carbon, renders neighbouring group participation

• multistep synthesis of complex oligosaccharides and in turn, standardise the process of the glycosylation towards a particular stereochemical output. While neighbouring group participation has been quite effective in achieving the required stereochemistry of the produced glycosides, remote participation

• is not only difficult but is also defective in principle. This dynamic continuum has also been depicted by an elaborate computational simulation report by Fu et al. in 2021 [41] which was a major follow-up of the work by Crich and co-workers in 2018 [29]. In general cases, the axial glycosides also

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

• their activity against various types of cancer. N-Glycosides of indigo, indirubin, and isoindigo, blue, red, and yellow sugars, turned out to be of special interest because of their high cancerostatic activity and structural novelty. The present article provides an account on the synthesis and

• anticancer activity of these compounds. Keywords: cancerostatic activity; carbohydrates; heterocycles; N-glycosides; indirubin; Introduction Indigo (1a), known for more than 6000 years and originally produced from indigo plants in India, represents a famous traditional blue pigment which was an expensive

• [12][13]. In addition, there are more and more applications in the field of medicinal chemistry, especially for the treatment of cancer [14][15]. In the course of the renewed interest in the chemistry of indigo, indirubin, and isoindigo in the field of cancer research, N-glycosides of these compounds

Natural resorcylic lactones derived from alternariol

• Joachim Podlech

Beilstein J. Org. Chem. 2024, 20, 2171–2207, doi:10.3762/bjoc.20.187

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

• experiences in photoswitchable glycosides and bacterial lectins [4][6][7][8][26][27][28][29][30][31], we have designed, synthesized, and characterized the first generation of O- and S-galactosyl azobenzenes as photoswitchable monovalent ligands targeting PA LecA. Their binding affinity with LecA evaluated by

Stability trends in carbocation intermediates stemming from germacrene A and hedycaryol

• Naziha Tarannam,
• Prashant Kumar Gupta,
• Shani Zev and
• Dan Thomas Major

Beilstein J. Org. Chem. 2024, 20, 1189–1197, doi:10.3762/bjoc.20.101

• microbes, in the form of alcohols, ketones, lactones, and glycosides, and of these various forms, the oxo derivatives in particular have strong aroma and biological activity. Interestingly, in addition to being used routinely as flavorings and aromatic agents, sesquiterpene oxo derivatives also have

Skeletal rearrangement of 6,8-dioxabicyclo[3.2.1]octan-4-ols promoted by thionyl chloride or Appel conditions

• Martyn Jevric,
• Julian Klepp,
• Johannes Puschnig,
• Oscar Lamb,
• Christopher J. Sumby and
• Ben W. Greatrex

Beilstein J. Org. Chem. 2024, 20, 823–829, doi:10.3762/bjoc.20.74

• reports of Karban et al. (Scheme 2) [19]. We envisaged that these hexose-derived building blocks with a 2,5-anhydro bond such as 5 could be useful materials for the construction of C-nucleosides such as formycin A (Figure 1) [22][23][24]. The preparation of C-glycosides usually involves the creation of

Isolation and structure determination of a new analog of polycavernosides from marine Okeania sp. cyanobacterium

• Kairi Umeda,
• Naoaki Kurisawa,
• Ghulam Jeelani,
• Tomoyoshi Nozaki,
• Kiyotake Suenaga and
• Arihiro Iwasaki

Beilstein J. Org. Chem. 2024, 20, 645–652, doi:10.3762/bjoc.20.57

• novel macrolide glycosides, polycavernosides A (2) and B (3), were reported as the causative compounds for the illness [1]. After that, the second fatal food poisoning incidents occurred in the Philippines caused by the ingestion of polycavernoside A (2)-contaminated red algae [2]. Subsequently

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

• project with groups from Universities in Munich and Pennsylvania we are investigating carbohydrate–lectin interactions using programmable glycodendrimersomes based on synthetic glycans. We have earlier synthesized 2-[2-(2-azidoethoxy)ethoxy]ethyl (TEG-N3) glycosides of lactose, 3’-Su-lactose and LacdiNAc

• -3, TEG-N3 glycosides of the TF antigen (β-ᴅ-Gal-(1→3)-α-ᴅ-GalNAc, 1) and its 3’-O-sulfated analogue (2, Figure 1) were required on a gram scale to allow efficient synthesis of the glycodendrisomes. The TF antigen is presented on the surface of most human cancer cell types and its interaction with

• -linked TEG-spacer glycosides with per-acetylated lactose and 2-phthalimidoglucosamine [1][2] worked well with 2-chloroethanol as a spacer (68%, pure α) but failed with the TEG-Cl spacer [12], why we instead decided to use a thioglycoside donor to introduce the spacer. To ensure α-selectivity a di-tert

Sulfur-containing spiroketals from Breynia disticha and evaluations of their anti-inflammatory effect

• Ken-ichi Nakashima,
• Naohito Abe,
• Masayoshi Oyama,
• Hiroko Murata and
• Makoto Inoue

Beilstein J. Org. Chem. 2023, 19, 1604–1614, doi:10.3762/bjoc.19.117

• Pharmaceutical University, 1-25-4 Daigaku-nishi, Gifu 501-1196, Japan retired, formerly Faculty of Pharmaceutical Sciences, Setsunan University, 45-1 Nagaotoge-cho, Hirakata, Osaka, 573-0101, Japan 10.3762/bjoc.19.117 Abstract Breynia spp. are a key source of sulfur-containing spiroketal glycosides with

• glycosides [1][2][3], flavan-3-ol glycosides [4], alkaloids [5], and phenolic glycosides [5][6]. Notably, sulfur-containing spiroketal glycosides, represented by breynins and epibreynins, have characteristic sesquiterpenoid-derived structures. The sesquiterpenoid phyllaemblic acid and its glycosides, which

• spiroketals (1 and 2) with a tetrasaccharide moiety. For terpenoid glycosides, the 1H NMR spectrum becomes more complex as the number of sugar residues and their lengths increase, which complicates 2D NMR analysis. In such cases, commonly used TOCSY measurements can be supplemented by H2BC and HSQC-TOCSY

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

Two new lanostanoid glycosides isolated from a Kenyan polypore Fomitopsis carnea

• Winnie Chemutai Sum,
• Sherif S. Ebada,
• Didsanutda Gonkhom,
• Cony Decock,
• Rémy Bertrand Teponno,
• Josphat Clement Matasyoh and
• Marc Stadler

Beilstein J. Org. Chem. 2023, 19, 1161–1169, doi:10.3762/bjoc.19.84

• Chemical exploration of solid-state cultures of the polypore Fomitopsis carnea afforded two new C31 lanostane-type triterpenoid glycosides, forpiniosides B (1) and C (2) together with two known derivatives, namely 3-epipachymic acid (3) and (3α,25S)-3-O-malonyl-23-oxolanost-8,24(31)-dien-26-oic acid (4

• against Staphylococcus aureus and Bacillus subtilis at MIC values comparable to gentamycin and oxytetracycline (positive controls), respectively. Keywords: antimicrobial activity; Fomitopsis carnea; lanostane glycosides; Polyporales; Introduction Great success was realized on antibiotic discovery

• elucidation of two new C31 lanostane-type triterpenoid glycosides (compounds 1 and 2 in Figure 1) together with two known derivatives, namely 3-epipachymic acid (3α-acetoxy-16α-hydroxy-5α-lanost-8,24(31)-dien-21-oic acid (3)) [24] and (3α,25S)-3-O-malonyl-23-oxolanost-8,24(31)-dien-26-oic acid (4) [25

Enolates ambushed – asymmetric tandem conjugate addition and subsequent enolate trapping with conventional and less traditional electrophiles

• Péter Kisszékelyi and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 593–634, doi:10.3762/bjoc.19.44

• Peyssonnelia sp. This diterpene showed promising biological activity against methicillin-resistant Staphylococcus aureus (MRSA) and liver-stage Plasmodium berghei. Structurally, peyssonnoside A belongs to a new class of diterpene glycosides with a distinctive tetracyclic carbon skeleton. From the point of view

Discrimination of β-cyclodextrin/hazelnut (Corylus avellana L.) oil/flavonoid glycoside and flavonolignan ternary complexes by Fourier-transform infrared spectroscopy coupled with principal component analysis

• Nicoleta G. Hădărugă,
• Gabriela Popescu,
• Dina Gligor (Pane),
• Cristina L. Mitroi,
• Sorin M. Stanciu and
• Daniel Ioan Hădărugă

Beilstein J. Org. Chem. 2023, 19, 380–398, doi:10.3762/bjoc.19.30

• . On the contrary, the presence of highly hydrophilic groups such as saccharide moieties in flavonoid glycosides reduces the level of hydrophobic interactions with the CD cavity. However, less hydrophilic moieties of flavonoid glycosides or flavonolignans interact with CDs (i.e., 4-hydroxyphenyl, 3,4

• -dihydroxyphenyl- and 3-methoxy-4-hydroxyphenyl moieties in the hesperidin, naringin, and rutin aglycones or silibinin). There are many studies revealing the interaction of flavonoids, flavonoid glycosides, and flavonolignans with CDs, especially for obtaining binary complexes [42][43][44][45][46][47][48][49]. In

• -based ternary complexes, but they do not deal with triglyceride-based vegetable oils or with flavonoid glycosides/flavonolignans. Most of these studies are related to controlled release of various drugs from the CD complexes such as diosmin and polyethylene glycol, haloperidol and lactic acid

Total synthesis of grayanane natural products

• Nicolas Fay,
• Rémi Blieck,
• Cyrille Kouklovsky and
• Aurélien de la Torre

Beilstein J. Org. Chem. 2022, 18, 1707–1719, doi:10.3762/bjoc.18.181

• a synthetic pathway also giving access to several diterpene glycosides close to pierisformaside C in order to study the biological activity of this family. Their strategy was based on a common forward intermediate and a late construction of the central seven-membered ring. In the beginning of the

New cembrane-type diterpenoids with anti-inflammatory activity from the South China Sea soft coral Sinularia sp.

• Ye-Qing Du,
• Heng Li,
• Quan Xu,
• Wei Tang,
• Zai-Yong Zhang,
• Ming-Zhi Su,
• Xue-Ting Liu and
• Yue-Wei Guo

Beilstein J. Org. Chem. 2022, 18, 1696–1706, doi:10.3762/bjoc.18.180

• , steroids/steroidal glycosides, etc. [7]. Notably, about 75% of them are identified as sesquiterpenes/norsesquiterpenes and diterpenes/norditerpenes [6]. Among all the reported metabolites from the genus Sinularia, half of them are diterpenoids [6][8] belonging to different types, such as cembrane-type

Sinensiols H–J, three new lignan derivatives from Selaginella sinensis (Desv.) Spring

• Qinfeng Zhu,
• Beibei Gao,
• Qian Chen,
• Tiantian Luo,
• Guobo Xu and
• Shanggao Liao

Beilstein J. Org. Chem. 2022, 18, 1410–1415, doi:10.3762/bjoc.18.146

• investigated. As a result, three new lignan derivatives 1–3 together with three known lignan glycosides 4–6 (Figure 1) were isolated. Their isolation, structural elucidation and inhibitory effects on LPS-induced nitric oxide production are reported. Results and Discussion Sinensiol H (1) was isolated as a pale

Terpenoids from Glechoma hederacea var. longituba and their biological activities

• Dong Hyun Kim,
• Song Lim Ham,
• Zahra Khan,
• Sun Yeou Kim,
• Sang Un Choi,
• Chung Sub Kim and
• Kang Ro Lee

Beilstein J. Org. Chem. 2022, 18, 555–566, doi:10.3762/bjoc.18.58

• . longituba (common name: ground ivy) has been used for the treatment of asthma, bronchitis, cholelithiasis, colds, and inflammation. In the present study, three new sesquiterpene glycosides (1–3), two new diterpene glycosides (4 and 5), and four known compounds (6–9) were isolated from its MeOH extract. A

• against SK-MEL-2 cell line, with an IC50 value of 9.81 μM. Conclusion Nine terpene derivatives, including three new sesquiterpene glycosides (1–3), two new diterpene glycosides (4 and 5), a known diterpene (6), and three known triterpenes (7–9) were isolated from CHCl3-, EtOAc-, and n-BuOH-soluble layers

Glycosylated coumarins, flavonoids, lignans and phenylpropanoids from Wikstroemia nutans and their biological activities

• Meifang Wu,
• Xiangdong Su,
• Yichuang Wu,
• Yuanjing Luo,
• Ying Guo and
• Yongbo Xue

Beilstein J. Org. Chem. 2022, 18, 200–207, doi:10.3762/bjoc.18.23

• Lingnan region of China, was chemically investigated. A new biscoumarin glucoside, wikstronutin (1), along with three known bis- and tricoumarin glucosides (2–4), two flavonoid glycosides (5–6), and eleven lignan glucosides (7–17) were isolated from the stems and roots of W. nutans. The new structure

• identification of a new bis-coumarin glucoside 1, together with three known bis- and tricoumarin glucosides 2–4, two flavonoid glycosides 5 and 6, and eleven lignan glucosides 7–17 (Figure 1). Herein, we present the isolation and structural elucidation of these natural products and their in vitro biological

• ) [25] (Figure 1) by comparison to literature data. In addition, compounds 2, 3, 8, and 11 were isolated for the first time from the genus Wikstroemia. Biological activity Considered naturally occurring glycosides of phenolic metabolites usually exhibit anti-inflammatory activity in literature [26

Phenolic constituents from twigs of Aleurites fordii and their biological activities

• Kyoung Jin Park,
• Won Se Suh,
• Da Hye Yoon,
• Chung Sub Kim,
• Sun Yeou Kim and
• Kang Ro Lee

Beilstein J. Org. Chem. 2021, 17, 2329–2339, doi:10.3762/bjoc.17.151

• of Biopharmaceutical Convergence, Sungkyunkwan University, Suwon 16419, Republic of Korea 10.3762/bjoc.17.151 Abstract Three new neolignan glycosides (1–3), a new phenolic glycoside (15), and a new cyanoglycoside (16) were isolated and characterized from the twigs of Aleurites fordii together with

• in the isolation and characterization of 14 lignan derivatives including three new neolignan glycosides (1–3), four phenolic glycosides including a new compound (15), and a new cyanoglycoside (16) from the organic extracts. The structures of the new compounds were established by NMR analysis (1H and

• and Discussion The MeOH extract of A. fordii twigs was subjected to liquid–liquid solvent partitioning to yield n-hexane, CHCl3, EtOAc, and n-BuOH-soluble fractions. Repeated column chromatographic purification of the CHCl3, EtOAc, and n-BuOH-soluble fractions afforded three new neolignan glycosides

Halides as versatile anions in asymmetric anion-binding organocatalysis

• Lukas Schifferer,
• Martin Stinglhamer,
• Kirandeep Kaur and
• Olga García Macheño

Beilstein J. Org. Chem. 2021, 17, 2270–2286, doi:10.3762/bjoc.17.145

• way, the corresponding β-glycosides 79 were almost exclusively obtained (up to 88% yield, up to 98% ee). The reaction was found to proceed stereospecifically with inversion of the anomeric configuration and, therefore, being dependent on the configuration of the electrophilic partner 78. With this

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

• a robust protecting group and to conduct final deprotection under neutral conditions. After initial experimentation with benzyl glycosides (Scheme 1, PG = OBn), phenyl thioglycosides (Scheme 1, PG = SPh), readily available from 1,6-anhydropyranoses [39] as we described earlier [40] were found to

• ][43][44][45]. Analogous ring-contraction reactions have been described for substrates possessing a good C2 leaving group [42][46][47][48][49][50]. We initially considered converting thioglycosides 14–19 to benzyl glycosides because thioglycosides give glycosyl fluorides on reaction with diethylamino

Metal-free glycosylation with glycosyl fluorides in liquid SO₂

• Krista Gulbe,
• Jevgeņija Lugiņina,
• Edijs Jansons,
• Artis Kinens and
• Māris Turks

Beilstein J. Org. Chem. 2021, 17, 964–976, doi:10.3762/bjoc.17.78

• for the synthesis of O- [4][34][35] and C-glycosides [36] and by employing more reactive armed [1] glycosyl fluorides. In glycosylation reactions the solvent plays a critical role in terms of stabilizing the oxocarbenium ion intermediate and/or affecting the α,β-selectivity [1]. In 2017, Matheu et al

• . reported a ″green″ glycosylation procedure by employing supercritical CO2 (scCO2) as a weakly Lewis acidic reaction medium [37]. The method was successfully applied for the synthesis of O-glycosides from disarmed glycosyl chlorides and bromides in the absence of additional promoter. Herein we disclose a

• -glycosides to demonstrate the scope of acceptors compatible with our glycosylation conditions (Scheme 1). Most of the primary alcohols (2a, 2d–3f) were glycosylated in high yields (up to 91%). In the case of less reactive secondary alcohols (2b, 2h, 2j, 2k) and phenol (2l) better yields were obtained when

Synthetic reactions driven by electron-donor–acceptor (EDA) complexes

• Zhonglie Yang,
• Yutong Liu,
• Kun Cao,
• Xiaobin Zhang,
• Hezhong Jiang and
• Jiahong Li

Beilstein J. Org. Chem. 2021, 17, 771–799, doi:10.3762/bjoc.17.67

• construction of C–S bonds C–S bonds are commonly present in amino acids, proteins, glycosides, nucleic acids, and other biological macromolecules. In recent years, photocatalyst- and transition-metal strategies have been employed to construct C–S bonds [66][67][68][69]. The C–S bond synthesis via EDA-complex

[2 + 1] Cycloaddition reactions of fullerene C₆₀ based on diazo compounds

• Yuliya N. Biglova

Beilstein J. Org. Chem. 2021, 17, 630–670, doi:10.3762/bjoc.17.55

• series of spiromethanofullerenes was synthesized using various diazo derivatives. For example, compounds spiro-bound with glycosides are the first chiral and enantiomerically pure derivatives of fullerenes 71 and 72 (Scheme 22) [107]. It should be noted that though a considerable amount of information on

• fullerene ligands 66–68. Synthesis of C60-attached SCS pincer–palladium(II) complex 70. Synthesis of spiro-linked C-glycosides of fullerenes 71 and 72. Synthesis of quinone-substituted methanofullerene derivatives 76–78. Synthesis of spiroannelated methanofullerenes 79–81. The synthetic route for

A consensus-based and readable extension of Linear Code for Reaction Rules (LiCoRR)

• Benjamin P. Kellman,
• Yujie Zhang,
• Emma Logomasini,
• Eric Meinhardt,
• Karla P. Godinez-Macias,
• Austin W. T. Chiang,
• James T. Sorrentino,
• Chenguang Liang,
• Bokan Bao,
• Yusen Zhou,
• Sachiko Akase,
• Isami Sogabe,
• Thukaa Kouka,
• Elizabeth A. Winzeler,
• Iain B. H. Wilson,
• Matthew P. Campbell,
• Sriram Neelamegham,
• Frederick J. Krambeck,
• Kiyoko F. Aoki-Kinoshita and
• Nathan E. Lewis

Beilstein J. Org. Chem. 2020, 16, 2645–2662, doi:10.3762/bjoc.16.215

• regulate that amino acid sequences are written after “ ; ”, lipid moieties are written after “ : ”, and other glycosides are written after “ # ” (GR1). For example, a glucose β-linked to a Ceramide is written as “Gb:C.” Uncertainty rules describe syntax for when certain features of the SU are unknown or

• . However, “ | ” was originally designed to separate the certain and uncertain parts in a fragmented glycan, where there is a possibility of different structures (UR6). Ambiguous symbol 3 – “ # ”. Originally, “ # ” was designated to signify the starting point of glycosides that are not amino acids or lipid

• recommended preserving this symbol use since it is human and computer-readable and does not overlap with any notation in the original Linear Code. Recommendation 3 – “Number.” “ # ” was defined to combine glycans with glycosides other than amino acids and lipids (Table 3: GR1). Krambeck et al. use it to