New α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions

• Iveta Chena Tichá,
• Simona Hybelbauerová and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2019, 15, 830–839, doi:10.3762/bjoc.15.80

Polyaminoazide mixtures for the synthesis of pH-responsive calixarene nanosponges

• Antonella Di Vincenzo,
• Antonio Palumbo Piccionello,
• Alberto Spinella,
• Delia Chillura Martino,
• Marco Russo and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2019, 15, 633–641, doi:10.3762/bjoc.15.59

• copolymers (CyCaNSs) [16][17][18], which showed pH-dependent sequestration abilities towards different model organic substrates. The latter NSs were easily synthesized by means of a CuAAC-type reaction [19][20][21] between a heptakisazido-β-cyclodextrin and a tetrakis(propargyloxy)calix[4]arene derivative

• with CyCaNSs. This fact was explained assuming that a diazidoalkane is a less effective reticulating agent than a heptakisazido-β-cyclodextrin, simply because of the lesser number of reactive azide groups present. Hence, we reasoned that the polymer network formation process could have been improved by

Aqueous olefin metathesis: recent developments and applications

• Valerio Sabatino and
• Thomas R. Ward

Beilstein J. Org. Chem. 2019, 15, 445–468, doi:10.3762/bjoc.15.39

• (Figure 1c) through host–guest interactions [61]. Chung and co-workers used a PEG-tethered adamantyl ligand for various metathesis reactions in water and DCM [62]. The authors showed that the catalyst can be easily removed by generating a host–guest complex between silica-grafted β-cyclodextrin and the

• through host–guest interaction with silica-gel-supported β-cyclodextrin. Selection of artificial metathases reported by Ward and co-workers (ArM 1 based on biotin–(strept)avidin technology and ArM 2 based on dative anchoring to hCAII). Artificial metathase based on covalent anchoring approach. α

Pathoblockers or antivirulence drugs as a new option for the treatment of bacterial infections

• Matthew B. Calvert,
• Varsha R. Jumde and
• Alexander Titz

Beilstein J. Org. Chem. 2018, 14, 2607–2617, doi:10.3762/bjoc.14.239

• FmlH (compounds 8 and 9) and Pseudomonas aeruginosa LecA (compounds 10–12). Mannosides and fucosides as inhibitors of P. aeruginosa LecB. β-Cyclodextrin-based antitoxin 19 against S. aureus α-hemolysin and the decavalent Shiga toxin inhibitors STARFISH (20) and DAISY (21). The mechanism of quorum

Functionalization of graphene: does the organic chemistry matter?

• Artur Kasprzak,
• Agnieszka Zuchowska and
• Magdalena Poplawska

Beilstein J. Org. Chem. 2018, 14, 2018–2026, doi:10.3762/bjoc.14.177

• infrared spectrum of the functionalized graphene-family materials; thus, XPS should be regarded as a supporting analysis, as many researchers have demonstrated (see, e.g., [21][28][29]). Interestingly, for a reaction that includes water molecules and a hydroxy group-bearing compound (β-cyclodextrin) [25

• presented analyses the RGO surface can be assumed to include the adsorbed β-cyclodextrin (RGO has been obtained via a reduction of GO using sodium borohydride). Finally, there is a misunderstanding regarding the structure of the product bearing the amide moiety, as the lack of evidence for the formation of

• [40], it was not clear how the ester bond between RGO and hydroxypropyl-β-cyclodextrin would form, as the changes observed in the infrared spectra cannot be regarded as direct evidence for the formation of such linkages (IR analyses: C=O for carboxyl of GO: 1745 cm−1, C=O coming from ester bond stated

Efficient catenane synthesis by cucurbit[6]uril-mediated azide–alkyne cycloaddition

• Antony Wing Hung Ng,
• Chi-Chung Yee,
• Kai Wang and
• Ho Yu Au-Yeung

Beilstein J. Org. Chem. 2018, 14, 1846–1853, doi:10.3762/bjoc.14.158

• favorably interact with these units could be introduced to give higher-order catenanes with multiple interlocked rings. As a preliminary study of high-order [n]catenane assembly using this approach, CBAAC of BP-N3 and DN-CC was repeated in the presence of 10 equivalents of β-cyclodextrin (β-CD), which is

β-Hydroxy sulfides and their syntheses

• Mokgethwa B. Marakalala,
• Edwin M. Mmutlane and
• Henok H. Kinfe

Beilstein J. Org. Chem. 2018, 14, 1668–1692, doi:10.3762/bjoc.14.143

• reported the use of β-cyclodextrin as a catalyst for the hydroxysulfurization of alkenes with thiophenols in neat water under atmospheric oxygen as shown in Scheme 26 [63]. As opposed to the usual acid-base type of catalysis, β-cyclodextrin having hydrophobic cavities catalyze reactions via formation of

Hyper-reticulated calixarene polymers: a new example of entirely synthetic nanosponge materials

• Alberto Spinella,
• Marco Russo,
• Antonella Di Vincenzo,
• Delia Chillura Martino and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2018, 14, 1498–1507, doi:10.3762/bjoc.14.127

• polymers obtained joining supramolecular host units, as the monomers, by means of a suitable reticulating agent. Up to date, the examples by far most studied are constituted by cyclodextrin-based nanosponges (CyNSs) [4][5], which can be synthesized by reacting native β-cyclodextrin with double

• ]) between a heptakis(6-azido-6-deoxy)-β-cyclodextrin and a tetrakis(propargyloxy)calix[4]arene [11][31][32]. In this way, a random disposition of the co-monomer units linked by 1,2,3-triazole units is achieved. The obtained CyCaNSs benefit from several advantages. First, the properties of the material can

• extending the reaction time up to 90 h. These observations can be easily explained considering that the diazides used for our purposes are much less effective reticulating agents as compared to the heptakis(6-azido-6-deoxy)-β-cyclodextrin used for the synthesis of CyCaNSs, simply because of the different

Mechanochemistry of nucleosides, nucleotides and related materials

• Olga Eguaogie,
• Joseph S. Vyle,
• Patrick F. Conlon,
• Manuela A. Gîlea and
• Yipei Liang

Beilstein J. Org. Chem. 2018, 14, 955–970, doi:10.3762/bjoc.14.81

• using mechanochemistry [94] and Rajamohan and co-workers described using a mortar and pestle to effect LAG of β-cyclodextrin with either inosine [95] or cytidine [96] in the presence of water. Weak complex formation was inferred by powder XRD for cytidine. Conclusion Access to reliable and reproducible

Crystal structure of the inclusion complex of cholesterol in β-cyclodextrin and molecular dynamics studies

• Elias Christoforides,
• Andreas Papaioannou and
• Kostas Bethanis

Beilstein J. Org. Chem. 2018, 14, 838–848, doi:10.3762/bjoc.14.69

• drug carriers and cell cholesterol removal agents for controlling cholesterol-related disorders [3] are of special interest. β-Cyclodextrin (β-CD, Figure 1b) is a cyclic polysaccharide consisting of seven α-(1->4)-linked α-D-glucopyranose units and is well known for its ability to form inclusion

• cholesterol molecule; (b) the β-cyclodextrin molecule. (a) Crystal structure of the inclusion compound of cholesterol in β-CD dimer. Water molecules are omitted for clarity. (b) The inclusion complex colored by atomic displacement parameters (U’s) using Mercury 3.9. The values of U increase from blue to red

Binding abilities of polyaminocyclodextrins: polarimetric investigations and biological assays

• Marco Russo,
• Daniele La Corte,
• Annalisa Pisciotta,
• Serena Riela,
• Rosa Alduina and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2017, 13, 2751–2763, doi:10.3762/bjoc.13.271

• ed. 18, 90128 Palermo, Italy 10.3762/bjoc.13.271 Abstract Three polyaminocyclodextrin materials, obtained by direct reaction between heptakis(6-deoxy-6-iodo)-β-cyclodextrin and the proper linear polyamines, were investigated for their binding properties, in order to assess their potential

• in the case of mono-[6-(3-dimethylamino)propylamino]-6-deoxy-β-cyclodextrin the first protonation step occurs on the farthest N atom with respect to the CD cavity [48]. Thus, it is reasonable to expect that the same applies also to the polyamine branches of our AmCDs, in such a way to minimize

Influence of the milling parameters on the nucleophilic substitution reaction of activated β-cyclodextrins

• László Jicsinszky,
• Kata Tuza,
• Giancarlo Cravotto,
• Andrea Porcheddu,
• Francesco Delogu and
• Evelina Colacino

Beilstein J. Org. Chem. 2017, 13, 1893–1899, doi:10.3762/bjoc.13.184

• Montpellier, Institut des Biomolécules Max Mousseron (IBMM) UMR5247 CNRS-UM-ENSCM, Université de Montpellier, cc1703, Place Eugène Bataillon, 34095 Montpellier Cedex 05, France 10.3762/bjoc.13.184 Abstract The present work focuses on the mechanochemical preparation of industrially important β-cyclodextrin

• . Acknowledgements This work was funded by the University of Turin (Fondi Ricerca Locale 2016). The “Teach Mob - Teaching Staff Mobility Programme 2016–2017” (University of Turin, Italy) is warmly acknowledged by EC and GC. The authors thank Roquette (Lestrem, France) for the kind gift of β-cyclodextrin hydrate. AP

β-Cyclodextrin- and adamantyl-substituted poly(acrylate) self-assembling aqueous networks designed for controlled complexation and release of small molecules

• Liang Yan,
• Duc-Truc Pham,
• Philip Clements,
• Stephen F. Lincoln,
• Jie Wang,
• Xuhong Guo and
• Christopher J. Easton

Beilstein J. Org. Chem. 2017, 13, 1879–1892, doi:10.3762/bjoc.13.183

• networks are formed between 8.8% 6A-(2-aminoethyl)amino-6A-deoxy-6A-β-cyclodextrin, β-CDen, randomly substituted poly(acrylate), PAAβ-CDen, and one of the 3.3% 1-(2-aminoethyl)amidoadamantyl, ADen, 3.0% 1-(6-aminohexyl)amidoadamantyl, ADhn, or 2.9% 1-(12-aminododecyl)amidoadamantyl, ADddn, randomly

• substituted poly(acrylate)s, PAAADen, PAAADhn and PAAADddn, respectively, such that the ratio of β-CDen to adamantyl substituents is ca. 3:1. The variation of the characteristics of the complexation of the dyes methyl red, methyl orange and ethyl orange in these three networks and by β-cyclodextrin, β-CD, and

• designed into the structure of aqueous networks formed between a β-cyclodextrin-substituted poly(acrylate) and three adamantyl-substituted poly(acrylate)s. Accordingly, we report an ITC, 1H NMR and UV–vis spectroscopic and rheological study of three self-assembling networks formed between the 8.8% 6A-(2

Molecular recognition of N-acetyltryptophan enantiomers by β-cyclodextrin

• Spyros D. Chatziefthimiou,
• Mario Inclán,
• Petros Giastas,
• Athanasios Papakyriakou,
• Konstantina Yannakopoulou and
• Irene M. Mavridis

Beilstein J. Org. Chem. 2017, 13, 1572–1582, doi:10.3762/bjoc.13.157

• 10.3762/bjoc.13.157 Abstract The enantioselectivity of β-cyclodextrin (β-CD) towards L- and D-N-acetyltryptophan (NAcTrp) has been studied in aqueous solution and the crystalline state. NMR studies in solution show that β-CD forms complexes of very similar but not identical geometry with both L- and D

• crystallization, as a consequence of accumulation of many soft host–guest interactions and of the imposed crystallographic order, thus resulting in very dissimilar propensity of each enantiomer to produce crystals with β-CD. Keywords: β-cyclodextrin; enantiomeric discrimination; N-acetyltryptophan; NMR; X-ray

Synthesis of oligonucleotides on a soluble support

• Harri Lönnberg

Beilstein J. Org. Chem. 2017, 13, 1368–1387, doi:10.3762/bjoc.13.134

• short ODNs from base-moiety-protected 5´-(1-methoxy-1-methylethyl)-2´-deoxyribonucleoside 3´-phosphoramidites on a fully methylated β-cyclodextrin support [60]. The 1-methoxy-1-methylethyl group may be removed by acid-catalyzed methanolysis approximately as readily as the DMTr group, but it gives only

One-pot synthesis of block-copolyrotaxanes through controlled rotaxa-polymerization

• Jessica Hilschmann,
• Gerhard Wenz and
• Gergely Kali

Beilstein J. Org. Chem. 2017, 13, 1310–1315, doi:10.3762/bjoc.13.127

• acrylate and an acrylamide in the presence of methylated β-cyclodextrin was employed for the first time to synthesize block-copolyrotaxanes. RAFT polymerizations started from a symmetrical bifunctional trithiocarbonate and gave rise to triblock-copolymers where the outer polyacrylate/polyacrylamide blocks

Glyco-gold nanoparticles: synthesis and applications

• Federica Compostella,
• Olimpia Pitirollo,
• Alessandro Silvestri and
• Laura Polito

Beilstein J. Org. Chem. 2017, 13, 1008–1021, doi:10.3762/bjoc.13.100

• showed that GAuNPs were still able to recognize specific lectin (peanut agglutinin, PNA) and human galectin-3 (Gal-3), exploiting multiple lactose residues displayed on gold surface. Moreover, due to the presence of the β-cyclodextrin cavity, these nanostructures worked as site-specific delivery systems

Cyclodextrins tethered with oligolactides – green synthesis and structural assessment

• Cristian Peptu,
• Mihaela Balan-Porcarasu,
• Alena Šišková,
• Ľudovít Škultéty and
• Jaroslav Mosnáček

Beilstein J. Org. Chem. 2017, 13, 779–792, doi:10.3762/bjoc.13.77

• of the esterified CDs was supported in Harada’s work [17] by comparing the NMR spectra with those obtained for a monoesterified β-cyclodextrin at C2 position (mono-2-O-(6-benzyloxypentanoyl)-β-cyclodextrin). The peak at 63.4 ppm was assigned as C2’ of the monosubstituted glucose ring belonging to

• mono-2-O-(6-benzyloxypentanoyl)-β-cyclodextrin. The peak at 64.4 ppm, observed in our experiment, was differently assigned using a DEPT135 experiment on β-CD-LA-F1 and F2 (Figure 6). In the DEPT135-NMR spectra the peaks at 60 and 64.4 ppm are in opposite phase compared to the CH and CH3 peaks

Inclusion complexes of β-cyclodextrin with tricyclic drugs: an X-ray diffraction, NMR and molecular dynamics study

• Franca Castiglione,
• Fabio Ganazzoli,
• Luciana Malpezzi,
• Andrea Mele,
• Walter Panzeri and
• Giuseppina Raffaini

Beilstein J. Org. Chem. 2017, 13, 714–719, doi:10.3762/bjoc.13.70

• 7, 20131 Milano, Italy 10.3762/bjoc.13.70 Abstract Tricyclic fused-ring cyclobenzaprine (1) and amitriptyline (2) form 1:1 inclusion complexes with β-cyclodextrin (β-CD) in the solid state and in water solution. Rotating frame NOE experiments (ROESY) showed the same geometry of inclusion for both 1

• . Keywords: amitriptyline; β-cyclodextrin; crystal structure; cyclobenzaprine; molecular dynamics simulations; NOE; Introduction The present paper reports on a multidisciplinary approach [1][2] based on single crystal X-ray diffraction, solution NMR spectroscopy and molecular dynamics (MD) simulations with

• explicit water to study the inclusion complexes of two tricyclic aromatic molecules – cyclobenzaprine (1) and amitriptyline (2, Figure 1) – with β-cyclodextrin (β-CD). Previous work already considered certain aspects of the interaction of 2 with β-CD [3][4][5][6][7][8], but no full characterization of the

Fluorescent carbon dots from mono- and polysaccharides: synthesis, properties and applications

• Stephen Hill and
• M. Carmen Galan

Beilstein J. Org. Chem. 2017, 13, 675–693, doi:10.3762/bjoc.13.67

• ) when compared to 36% release at pH 7 and 27% at pH 12. In order to improve the drug delivery profile of the complex, the authors developed a β-cyclodextrin/tetracycline (β-TC) host–guest inclusion complex, which allows a second “barrier” of release. The pre-formulated β-TC complex was loaded onto the

• their surface. The PL intensity of the CDs was modified in a linear manner with Ag+ concentrations, and as such the nanoparticles could be utilised as a fluorescence probe to detect Ag+ in solution up to concentrations of 0–25 μM. β-Cyclodextrin has also been utilised in the synthesis of CDs using a

• surface passivation and inorganic dehydration method. The groups of Yang and Teo et al. demonstrated that the synthesis of excitation-independent green emissive CDs could be achieved through the reaction of β-cyclodextrin in the presence of oligoethyleneimine (OEI) and phosphoric acid under thermolysis

Novel β-cyclodextrin–eosin conjugates

• Gábor Benkovics,
• Damien Afonso,
• András Darcsi,
• Szabolcs Béni,
• Sabrina Conoci,
• Éva Fenyvesi,
• Lajos Szente,
• Milo Malanga and
• Salvatore Sortino

Beilstein J. Org. Chem. 2017, 13, 543–551, doi:10.3762/bjoc.13.52

• /bjoc.13.52 Abstract Eosin B (EoB) and eosin Y (EoY), two xanthene dye derivatives with photosensitizing ability were prepared in high purity through an improved synthetic route. The dyes were grafted to a 6-monoamino-β-cyclodextrin scaffold under mild reaction conditions through a stable amide linkage

• -cyclodextrin–EoY conjugate retains both the fluorescence properties and the capability to photogenerate singlet oxygen of the unbound chromophore. In contrast, the corresponding β-cyclodextrin–EoB conjugate did not show either relevant emission or photosensitizing activity probably due to aggregation in

• using the coupling agent 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride. The molecular conjugates, well soluble in aqueous medium, were extensively characterized by 1D and 2D NMR spectroscopy and mass spectrometry. Preliminary spectroscopic investigations showed that the β

Structure–efficiency relationships of cyclodextrin scavengers in the hydrolytic degradation of organophosphorus compounds

• Sophie Letort,
• Michaël Bosco,
• Benedetta Cornelio,
• Frédérique Brégier,
• Sébastien Daulon,
• Géraldine Gouhier and
• François Estour

Beilstein J. Org. Chem. 2017, 13, 417–427, doi:10.3762/bjoc.13.45

• study focusing on the impact of covalently bound functional groups to macrocyclic β-cyclodextrin that are involved in the OP hydrolysis. Four new derivatives 2–5 were prepared (Figure 3) for this purpose. Compared to analog 1, scavenger 2 has a longer linker between the iodosobenzoate group and the

• methylated-β-cyclodextrin scaffold whilst scavenger 3 is characterized by a longer linker binding the imidazole ring to the CD derivative. Finally, compounds 4 and 5 are analogs of 2 bearing only one of these groups, either the α nucleophile or the imidazole ring, respectively. All five derivatives 1–5 were

• scavengers (with the groups covalently attached to the macrocycle) and with mixtures of heptakis(2,3,6-trimethyl)-β-cyclodextrin (TRIMEB) with 2-iodosobenzoic acid and/or imidazole, respectively. In addition, the degradation properties of the newly synthesized CD derivatives against methyl parathion and

Dynamics and interactions of ibuprofen in cyclodextrin nanosponges by solid-state NMR spectroscopy

• Monica Ferro,
• Franca Castiglione,
• Nadia Pastori,
• Carlo Punta,
• Lucio Melone,
• Walter Panzeri,
• Barbara Rossi,
• Francesco Trotta and
• Andrea Mele

Beilstein J. Org. Chem. 2017, 13, 182–194, doi:10.3762/bjoc.13.21

• of Chemistry, University of Torino, Via Pietro Giuria 7, 10125 Torino, Italy 10.3762/bjoc.13.21 Abstract Two different formulations of cyclodextrin nanosponges (CDNS), obtained by polycondensation of β-cyclodextrin with ethylenediaminetetraacetic acid dianhydride (EDTAn), were treated with aqueous

• ) was encapsulated in cyclodextrin nanosponges (CDNS) obtained by cross-linking of β-cyclodextrin with ethylenediaminetetraacetic acid dianhydride (EDTAn) in two different preparations: CDNS(1:4) and CDNS(1:8), where the 1:n notation indicates the CD to EDTAn molar ratio used for the synthesis. The

• monomeric β-cyclodextrin are listed [26]. All the carbon atoms revealed short T1ρ values in the range of 3–5 ms and similar for β-CD C atoms and the carbonyl atom of the cross-linker, suggesting that their chemical environments are equally proximate to the 1H reservoirs. This result is indicative of the

Nucleophilic displacement reactions of 5′-derivatised nucleosides in a vibration ball mill

• Olga Eguaogie,
• Patrick F. Conlon,
• Francesco Ravalico,
• Jamie S. T. Sweet,
• Thomas B. Elder,
• Louis P. Conway,
• Marc E. Lennon,
• David R. W. Hodgson and
• Joseph S. Vyle

Beilstein J. Org. Chem. 2017, 13, 87–92, doi:10.3762/bjoc.13.11

• liquid [13][14][15]. Recently, Jicsinszky et al. described using a planetary ball mill to perform substitution reactions of 6I-O-(p-toluenesulfonyl)-β-cyclodextrin (Ts-β-CD) with azide, halide or thiolate nucleophiles and thereby avoided intramolecular cyclisation (commonly found under solution-phase

Synthesis of multi-lactose-appended β-cyclodextrin and its cholesterol-lowering effects in Niemann–Pick type C disease-like HepG2 cells

• Keiichi Motoyama,
• Rena Nishiyama,
• Yuki Maeda,
• Taishi Higashi,
• Yoichi Ishitsuka,
• Yuki Kondo,
• Tetsumi Irie,
• Takumi Era and
• Hidetoshi Arima

Beilstein J. Org. Chem. 2017, 13, 10–18, doi:10.3762/bjoc.13.2

• -cyclodextrin (HP-β-CD). HP-β-CD is effective in the treatment of hepatosplenomegaly in NPC disease, albeit at a very high dose. One of the methods to reduce the required dose of HP-β-CD for treatment of NPC is to actively targeting hepatocytes with β-cyclodextrin (β-CD). The aim of the present study was to

• , and bioavailability of drugs. CDs improve the above properties of drugs through complex formation, when formulated as injectable solutions, sprays, eye drops, powders, and tablets [7][8]. In recent years, the efficacy of 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) in the treatment of the NPC disease has

• Niemann–Pick type C (NPC) disease, characterized by intracellular accumulation of unesterified cholesterol and other lipids owing to defects in two proteins NPC1 and NPC2, causes neurodegeneration and other fatal neurovisceral symptoms. Currently, treatment of NPC involves the use of 2-hydroxypropyl-β