Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

• –face interaction between the face of the anthracene bridge present in the cyclophane molecule and the edge of the host molecule. Bukownik and Wilcox [89] have synthesized macrocyclic C-glycosyl compounds, and obtained the chiral and water-soluble cyclophane 46. They reported on the use of its

Interactions between tetrathiafulvalene units in dimeric structures – the influence of cyclic cores

• Huixin Jiang,
• Virginia Mazzanti,
• Christian R. Parker,
• Søren Lindbæk Broman,
• Jens Heide Wallberg,
• Karol Lušpai,
• Adam Brincko,
• Henrik G. Kjaergaard,
• Anders Kadziola,
• Peter Rapta,
• Ole Hammerich and
• Mogens Brøndsted Nielsen

Beilstein J. Org. Chem. 2015, 11, 930–948, doi:10.3762/bjoc.11.104

• TTF dimer tetracations. As already extensively discussed in [32] concerning the redox properties of self-assembled polyelectrolyte multilayers, consisting of well-defined water-soluble electronically conducting poly-3-(30-thienyloxy)propyltriethylammonium, the spinless doubly charged species can be

Regulation of integrin and growth factor signaling in biomaterials for osteodifferentiation

• Qiang Wei,
• Theresa L. M. Pohl,
• Anja Seckinger,
• Joachim P. Spatz and
• Elisabetta A. Cavalcanti-Adam

Beilstein J. Org. Chem. 2015, 11, 773–783, doi:10.3762/bjoc.11.87

• , which can stimulate cell growth and differentiation, have also been employed for bone treatment [8][9]. Growth factors are water soluble proteins embedded in the ECM network mainly via non-covalent interactions with glycosaminoglycanes (GAG) [10]. Therefore, the ECM serves as a reservoir by establishing

Design, synthesis and photochemical properties of the first examples of iminosugar clusters based on fluorescent cores

• Mathieu L. Lepage,
• Antoine Mirloup,
• Manon Ripoll,
• Fabien Stauffert,
• Anne Bodlenner,
• Raymond Ziessel and
• Philippe Compain

Beilstein J. Org. Chem. 2015, 11, 659–667, doi:10.3762/bjoc.11.74

• fluorophore core is naturally primordial for the design of photostable, water-soluble and biocompatible probes with the required photophysical properties. An additional challenge is that, as the central core of a multivalent system, the fluorophore structure defines also its valency, size and shape

• resulting from the cleavage of the carbon–boron bond in 6b. The same experimental protocol was applied to functionalized BODIPY 6a, leading to the desired trivalent cluster 12a in 83% yield. O-Deacetylation of compounds 12 using anion exchange Amberlite IRA-400 (OH−) resin provided the desired water-soluble

• . To our knowledge these are the first examples of the use of BODIPY or pyrene as a scaffold to display multivalent ligands. Although the trivalent BODIPY-derived DNJ clusters are water soluble, a co-solvent is necessary to dissolve the tetravalent pyrene-derived DNJ clusters in water. Photophysical

Synthesis of multivalent carbohydrate mimetics with aminopolyol end groups and their evaluation as L-selectin inhibitors

• Joana Salta,
• Jens Dernedde and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2015, 11, 638–646, doi:10.3762/bjoc.11.72

• similar to those with the related unsulfated amine derivatives previously reported [24]. We expected that all polysulfated amides are water soluble at concentrations suitable for the SPR assay, but disappointingly amides 31 and 33 (Scheme 5 and Scheme 6) were not sufficiently soluble and therefore no

Matsuda–Heck reaction with arenediazonium tosylates in water

• Ksenia V. Kutonova,
• Marina E. Trusova,
• Andrey V. Stankevich,
• Pavel S. Postnikov and
• Victor D. Filimonov

Beilstein J. Org. Chem. 2015, 11, 358–362, doi:10.3762/bjoc.11.41

• (Table 2, entries 14–18). Conclusion In summary, a fast, simple, eco-friendly Heck arylation protocol in water with stable, safe and water-soluble arenediazonium tosylates is described. It was shown that in most cases the microwave irradiation significantly decreases the reaction time to several minutes

Formation of nanoparticles by cooperative inclusion between (S)-camptothecin-modified dextrans and β-cyclodextrin polymers

• Thorbjørn Terndrup Nielsen,
• Catherine Amiel,
• Laurent Duroux,
• Kim Lambertsen Larsen,
• Lars Wagner Städe,
• Reinhard Wimmer and
• Véronique Wintgens

Beilstein J. Org. Chem. 2015, 11, 147–154, doi:10.3762/bjoc.11.14

• the inactive and toxic carboxylate form. A way to circumvent these drawbacks can be to conjugate the CPT to hydrophilic polymers and hereby creating a water-soluble polymeric CPT prodrug whereby the apparent aqueous solubility of the drug is increased. Furthermore, modification of the CPT hydroxy

Effects of RAMEA-complexed polyunsaturated fatty acids on the response of human dendritic cells to inflammatory signals

• Éva Rajnavölgyi,
• Renáta Laczik,
• Viktor Kun,
• Lajos Szente and
• Éva Fenyvesi

Beilstein J. Org. Chem. 2014, 10, 3152–3160, doi:10.3762/bjoc.10.332

• depends on the type, number and position of the substituents [18][19]. For example, water soluble palmitic acid and myristic acid complexed by RAMEB could be used for cultivation of otherwise non-cultivable leprosy-derived psychrophilic mycobacteria [20]. The methylated β-CDs are used as cholesterol

• depleting agents to disrupt caveolae and lipid rafts in the cell membrane as well as for replenishment of cholesterol in the form of water-soluble cholesterol/methyl β-CD complex to clarify the role of lipid rafts in various cellular processes [21][22]. For instance, DHA exerted anti-inflammatory effects

Release of β-galactosidase from poloxamine/α-cyclodextrin hydrogels

• César A. Estévez,
• José Ramón Isasi,
• Eneko Larrañeta and
• Itziar Vélaz

Beilstein J. Org. Chem. 2014, 10, 3127–3135, doi:10.3762/bjoc.10.330

• causing increased contact with the medium. Thus, the lactase activity data in acidic media for the commercial tablets could not be collected. The type of drug, its polymorphism, crystallinity, particle size and other factors can influence the release kinetics. A water-soluble drug incorporated into a

Conjugates of methylated cyclodextrin derivatives and hydroxyethyl starch (HES): Synthesis, cytotoxicity and inclusion of anaesthetic actives

• Lisa Markenstein,
• Antje Appelt-Menzel,
• Marco Metzger and
• Gerhard Wenz

Beilstein J. Org. Chem. 2014, 10, 3087–3096, doi:10.3762/bjoc.10.325

• /bjoc.10.325 Abstract The mono-6-deoxy-6-azides of 2,6-di-O-methyl-β-cyclodextrin (DIMEB) and randomly methylated-β-cyclodextrin (RAMEB) were conjugated to propargylated hydroxyethyl starch (HES) by Cu+-catalysed [2 + 3] cycloaddition. The resulting water soluble polymers showed lower critical solution

• propargyl ether leading to a highly water soluble polymer 3 with DSHES(propargyl) = 0.55. Coupling of the CD azides 1a and 1b to the propargylated HES was performed by Cu+-catalyzed [2 + 3] cycloaddition, the so-called click reaction, leading to the corresponding triazol groups (Scheme 3). The standard

Synthetic strategies for the fluorescent labeling of epichlorohydrin-branched cyclodextrin polymers

• Milo Malanga,
• Mihály Bálint,
• István Puskás,
• Kata Tuza,
• Tamás Sohajda,
• László Jicsinszky,
• Lajos Szente and
• Éva Fenyvesi

Beilstein J. Org. Chem. 2014, 10, 3007–3018, doi:10.3762/bjoc.10.319

• prepared either in well water-soluble form or as gels of high swelling. Two versatile synthetic strategies for introducing a fluorescent tag (rhodamine, fluorescein, nitrobenzofuran or coumarin) into the water-soluble epichlorohydrin branched cyclodextrin polymers were worked out and compared. The

• , the process of purification and the characterization for the epichlorohydrin branched water soluble polymers obtained from native cyclodextrins are well established processes [9][10]. The characteristics of the cyclodextrin polymers can be modulated by appending neutral or ionic functional groups

• introduction of methyl groups into the CD polymers generates structures with peculiar properties, such as enhanced solubility and solubilizing effect, although only a few examples are found in the literature [14][15]. The introduction of a fluorescent tag into a water-soluble epichlorohydrin-branched CD

Synthesis of uniform cyclodextrin thioethers to transport hydrophobic drugs

• Lisa F. Becker,
• Dennis H. Schwarz and
• Gerhard Wenz

Beilstein J. Org. Chem. 2014, 10, 2920–2927, doi:10.3762/bjoc.10.310

• displacement reactions starting from the corresponding per-(6-deoxy-6-bromo)cyclodextrins. Further modification of all 2-OH positions by etherification with iodo terminated triethylene glycol monomethyl ether (and tetraethylene glycol monomethyl ether, respectively) furnished water-soluble hosts. Especially

• -, β- and γ-CD, respectively [1]. CDs are well known to increase the bioavailability of active pharmaceutical ingredients (APIs) [2][3], and they are readily available in pharmaceutical purity and industrial quantities. Furthermore, they are water soluble and regarded as non-toxic in case of α- and γ

• ]. The reaction was performed in DMF solution leading to the corresponding thioethers 1b1/1b2 in excellent yields (up to 92%). Afterwards, these thioethers 1b1/1b2 were hydroxyethylated with ethylene carbonate to the water soluble derivatives 2b1/2b2 according to Mazzaglia et al. [43]. The ESI MS of 2b1

A study on the inhibitory mechanism for cholesterol absorption by α-cyclodextrin administration

• Takahiro Furune,
• Naoko Ikuta,
• Yoshiyuki Ishida,
• Hinako Okamoto,
• Daisuke Nakata,
• Keiji Terao and
• Norihiro Sakamoto

Beilstein J. Org. Chem. 2014, 10, 2827–2835, doi:10.3762/bjoc.10.300

• found to decrease through lecithin precipitation caused by the addition of α-CD, in a dose-dependent manner. Furthermore, each of several other water-soluble dietary fibers was added to the FeSSIF, and no precipitate was generated. Conclusion: This study suggests that α-CD decreases the micellar

• solubility of cholesterol in the lumen of the small intestine via the precipitation of lecithin from bile salt micelles by complex formation with α-CD. It further indicates that the lecithin precipitation effect on the bile salt micelles by α-CD addition clearly differs from addition of other water-soluble

• various effects on stabilization of fatty acids, flavor retention and emulsion formation of triglycerides via the formation of an inclusion complex [4][6][7][8]. α-CD is not used only as an encapsulation agent but also as a water-soluble dietary fiber. Furthermore, it has been reported that α-CD intake

Synthesis of an organic-soluble π-conjugated [3]rotaxane via rotation of glucopyranose units in permethylated β-cyclodextrin

• Jun Terao,
• Yohei Konoshima,
• Akitoshi Matono,
• Hiroshi Masai,
• Tetsuaki Fujihara and
• Yasushi Tsuji

Beilstein J. Org. Chem. 2014, 10, 2800–2808, doi:10.3762/bjoc.10.297

• -phenylene) [23] and oligothiophene [24] with linked [3]rotaxane structures via the flipping phenomenon [25]. Results and Discussion Kano and co-workers reported the synthesis of a linked pseudo [3]rotaxane involving a water-soluble porphyrin unit with carboxylate groups as the guest unit by double self

• -inclusion via sequential flipping of permethylated β-cyclodextrin (PM β-CD) in water [26]. To synthesize an organic-soluble insulated π-conjugated rotaxane, we applied this technique to the synthesis of an insulated porphyrin without water-soluble functional groups. The synthetic route to the PM β-CD based

Binding mode and free energy prediction of fisetin/β-cyclodextrin inclusion complexes

• Bodee Nutho,
• Wasinee Khuntawee,
• Chompoonut Rungnim,
• Piamsook Pongsawasdi,
• Peter Wolschann,
• Alfred Karpfen,
• Nawee Kungwan and
• Thanyada Rungrotmongkol

Beilstein J. Org. Chem. 2014, 10, 2789–2799, doi:10.3762/bjoc.10.296

• applications, β-CD has been mostly used as a drug carrier, stabilizer and additive by the formation of host–guest complexes with increased solubility and consequently better bioavailability of low water soluble organic compounds (i.e., drugs) [20][21][22][23]. The inclusion complex can also improve ligand

Cyclodextrin-grafted polymers functionalized with phosphanes: a new tool for aqueous organometallic catalysis

• Jonathan Potier,
• Stéphane Menuel,
• David Mathiron,
• Véronique Bonnet,
• Frédéric Hapiot and
• Eric Monflier

Beilstein J. Org. Chem. 2014, 10, 2642–2648, doi:10.3762/bjoc.10.276

• CNRS 3517, 33 rue St Leu, 80039 Amiens, France 10.3762/bjoc.10.276 Abstract New cyclodextrin (CD)-grafted polymers functionalized with water-soluble phosphanes were synthesized in three steps starting from polyNAS. Once characterized by NMR spectroscopy and size-exclusion chromatography, they were

• into linear butyraldehyde using a rhodium catalyst immobilized in the aqueous phase by coordination of the famous water-soluble ligand TPPTS (trisodium salt of the trisulfonated triphenylphosphane) [2]. However, while propene is partially soluble in water, terminal alkenes containing more than 6 carbon

• were added separately in the aqueous catalytic solution in our previous study, we synthesized a CD-substituted polymer functionalized with water-soluble phosphanes. The idea was to increase the local concentration of interfacial additive and phosphane-coordinated Rh catalyst at the aqueous/oganic

Encapsulation of biocides by cyclodextrins: toward synergistic effects against pathogens

• Véronique Nardello-Rataj and
• Loïc Leclercq

Beilstein J. Org. Chem. 2014, 10, 2603–2622, doi:10.3762/bjoc.10.273

• hosts are probably the cyclodextrins (CDs). CDs can form water-soluble complexes with numerous hydrophobic compounds. They have been widespread used in medicine, drug delivery and are of interest for the biocides encapsulation. Indeed, this enables the development of more or less complex systems that

• -hydroxybenzoate, benzyl alcohol, 2-phenoxyethanol) [45]. The authors established a clear relationship between the binding constants and the antimicrobial activity of the preservatives on various strains: Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli and C. albicans. Indeed, highly water-soluble

• some explanations for the cells lysis. Due to their structures, these amphiphilic biocides are more water-soluble than organic preservatives. Therefore, their encapsulation by CDs is generally not used to enhance their water-solubility. i) Antagonistic effect In 1992, Simpson reported that the

Synthesis and characterization of a hyper-branched water-soluble β-cyclodextrin polymer

• Francesco Trotta,
• Fabrizio Caldera,
• Roberta Cavalli,
• Andrea Mele,
• Carlo Punta,
• Lucio Melone,
• Franca Castiglione,
• Barbara Rossi,
• Monica Ferro,
• Vincenza Crupi,
• Domenico Majolino,
• Valentina Venuti and
• Dominique Scalarone

Beilstein J. Org. Chem. 2014, 10, 2586–2593, doi:10.3762/bjoc.10.271

• hyper-branched water-soluble polymer was synthesized by reacting β-cyclodextrin with pyromellitic dianhydride beyond the critical conditions that allow the phenomenon of gelation to occur. The molar ratio between the monomers is a crucial parameter that rules the gelation process. Nevertheless, the

• polymer were assessed by solubility tests, ultrafiltration experiments, size exclusion chromatography and Raman or FTIR spectroscopy. The new water soluble hyper-branched polymer shows complexing properties towards organic molecules and inorganic cations. Results and Discussion Synthesis and chemical

• cross-linker/β-CD molar ratio suggest that these water-soluble polymers are more likely composed of hyper-branched structures, rather than linear chains. This is consistent with the infrared and Raman analysis discussed below. In Figure 4a,b the Raman and FTIR–ATR spectra of the branched β-CD-based

Host–guest-driven color change in water: influence of cyclodextrin on the structure of a copper complex of poly((4-hydroxy-3-(pyridin-3-yldiazenyl)phenethyl)methacrylamide-co-dimethylacrylamide)

• Nils Retzmann,
• Gero Maatz and
• Helmut Ritter

Beilstein J. Org. Chem. 2014, 10, 2480–2483, doi:10.3762/bjoc.10.259

• of CD–dye hydrogels by addition of metal ions, as well as the sensing of copper ions using cyclodextrin–dye rotaxane [10][11]. Herewith we thus wish to describe our recent results about the synthesis of a water-soluble polymer bearing a novel azo dye and the presumed formation of complexes with Cu

• -(4-hydroxy-3-(pyridin-3-yldiazenyl)phenethyl) methacrylamide (5) and preparation of its water-soluble copolymer 7. Supporting Information Supporting Information File 434: Experimental.

Towards the sequence-specific multivalent molecular recognition of cyclodextrin oligomers

• Michael Kurlemann and
• Bart Jan Ravoo

Beilstein J. Org. Chem. 2014, 10, 2428–2440, doi:10.3762/bjoc.10.253

• Supporting Information File 1). The di- and trivalent guest strands 8–14 (Figure 1C, D) were synthesized by solid phase peptide synthesis using a standard Fmoc-protocol (Figure 3). Therefore the serine derivatives 15 and 16 (Figure 1E) and a water-soluble linker molecule were used. The purity of the guest

A versatile δ-aminolevulinic acid (ΑLA)-cyclodextrin bimodal conjugate-prodrug for PDT applications with the help of intracellular chemistry

• Chrysie Aggelidou,
• Theodossis A. Theodossiou,
• Antonio Ricardo Gonçalves,
• Mariza Lampropoulou and
• Konstantina Yannakopoulou

Beilstein J. Org. Chem. 2014, 10, 2414–2420, doi:10.3762/bjoc.10.251

• , Aghia Paraskevi Attikis, 15310 Greece. Tel. +30210 6503796, Fax: +30 210 6511766 10.3762/bjoc.10.251 Abstract Grafting of δ-aminolevulinic acid (1) moieties on the narrow periphery of a β-cyclodextrin (β-CD) derivative through hydrolysable bonds was implemented, in order to generate a water-soluble

• , molecular/drug carrier with the capacity to undergo intracellular transformation into protoporphyrin IX (PpIX), an endogenous powerful photosensitizer for photodynamic therapy (PDT). The water-soluble derivative 2 was prepared by esterifying δ-azidolevulinic acid with heptakis(6-hydroxyethylamino-6-deoxy)-β

• -cyclodextrin, with an average degree of substitution, DS = 3. Delivery of water-soluble, colorless 2 to cells resulted in intense red fluorescence registered by confocal microscopy, evidently due to the engagement of the intracellular machinery towards formation of PpIX. Conjugate 2 was further complexed with

Oligomerization of optically active N-(4-hydroxyphenyl)mandelamide in the presence of β-cyclodextrin and the minor role of chirality

• Helmut Ritter,
• Antonia Stöhr and
• Philippe Favresse

Beilstein J. Org. Chem. 2014, 10, 2361–2366, doi:10.3762/bjoc.10.246

• -cyclodextrin (CD) allows the oxidative coupling of poor water soluble phenol derivatives via complexation without using of organic solvents [6][7][8]. However, to the best of our knowledge, there were no studies published dealing with the potential enantioselective control of enzyme catalyzed oligomerization

• of both enantiomers of N-(4-hydroxyphenyl)mandelamide (1) were obtained though oxidative coupling with peroxidase and laccase and also via oligomerization with iron(II)-salen and hydrogen peroxide as a catalyzing system. In the presence of RAMEB-CD it was possible to oligomerize the poorly water

• soluble enantiomers of 1 without using organic solvents. In the case of oligomerization with laccase the monomeric residual keeps racemic. In contrast to this, with peroxidase the (S)-enantiomer of 1 slightly enriches the monomeric residual. RAMEB-CD promotes the (S)-enantiomer of 1 which was more readily

Molecular ordering at electrified interfaces: Template and potential effects

• Thanh Hai Phan and
• Klaus Wandelt

Beilstein J. Org. Chem. 2014, 10, 2243–2254, doi:10.3762/bjoc.10.233

• also more economic than operating a vacuum evaporation system, in particular if the organic building blocks come in water-soluble form. In principle, the self-organization process of molecular adsorbates is driven by the interplay between adsorbate–adsorbate and adsorbate–substrate interactions. While

Photo, thermal and chemical degradation of riboflavin

• Muhammad Ali Sheraz,
• Sadia Hafeez Kazi,
• Sofia Ahmed,
• Zubair Anwar and
• Iqbal Ahmad

Beilstein J. Org. Chem. 2014, 10, 1999–2012, doi:10.3762/bjoc.10.208

• , belongs to the class of water-soluble vitamins and is widely present in a variety of food products. It is sensitive to light and high temperature, and therefore, needs a consideration of these factors for its stability in food products and pharmaceutical preparations. A number of other factors have also

• photodegradation of RF has also been studied in various alcohols and alcohol/water mixtures alone [83] or with a water-soluble analog of vitamin E, namely trolox [84]. A photolysis study on four derivatives of RF performed in methanolic solutions identified a more efficient photodegradation in anaerobic

Sacrolide A, a new antimicrobial and cytotoxic oxylipin macrolide from the edible cyanobacterium Aphanothece sacrum

• Naoya Oku,
• Miyako Matsumoto,
• Kohsuke Yonejima,
• Keijiroh Tansei and
• Yasuhiro Igarashi

Beilstein J. Org. Chem. 2014, 10, 1808–1816, doi:10.3762/bjoc.10.190

• fractionation resulted in the discovery of a new macrolactonic oxylipin, sacrolide A (1, Figure 1). Results and Discussion A. sacrum (500 g) was extracted with EtOH, and the combined extract was fractionated by solvent partitioning into n-hexane-, 10% aqueous MeOH-, 1-BuOH-, and water-soluble fractions