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Search for "supramolecular properties" in Full Text gives 13 result(s) in Beilstein Journal of Organic Chemistry.
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
- challenging to design small molecule catalysts that resemble anion-binding properties of enzymes. Hence, a major challenge of small organic receptors to mimic nature’s capability of binding to the targeted anions resides in the supramolecular properties of enzymes and co-factors to form exact matching binding
Graphical Abstract
Figure 1: a) Binding interactions in the chloride channel of E. coli. and b) examples of chloride, cyanide, n...
Figure 2: a) H-bond vs anion-binding catalysis and b) activation modes in anion-binding catalysis.
Scheme 1: First proposed anion-binding mechanism in the thiourea-catalyzed acetalization of benzaldehyde.
Scheme 2: a) Thiourea-catalyzed enantioselective acyl-Pictet–Spengler reaction of tryptamine-derived imines 4...
Scheme 3: Proposed mechanism of the thiourea-catalyzed enantioselective Pictet–Spengler reaction of hydroxyla...
Scheme 4: a) Thiourea-catalyzed intramolecular Pictet–Spengler-type cyclization of hydroxylactam-derived N-ac...
Scheme 5: Enantioselective Reissert-type reactions of a) (iso)quinolines with silyl ketene acetals, and b) vi...
Figure 3: Role of the counter-anion: a) Anion acting as a spectator and b) anion participating directly as th...
Scheme 6: Enantioselective selenocyclization catalyzed by squaramide 28.
Scheme 7: Desymmetrization of meso-aziridines catalyzed by bifunctional thiourea catalyst 31.
Scheme 8: Anion-binding-catalyzed desymmetrization of a) meso-aziridines catalyzed by chiral triazolium catal...
Scheme 9: Bis-urea-catalyzed enantioselective fluorination of a) β-bromosulfides and b) β-haloamines by Gouve...
Scheme 10: a) Bifunctional thiourea anion-binding – basic/nucleophilic catalysts. Selected applications in b) ...
Scheme 11: Thiourea-catalyzed enantioselective polycyclization reaction of hydroxylactams 51 through cation–π ...
Scheme 12: Enantioselective aza-Sakurai cyclization of hydroxylactams 56 implicating additional cation–π and L...
Scheme 13: Enantioselective tail-to-head cyclization of neryl chloride derivatives.
Scheme 14: Cation–π interactions in anion binding-catalyzed asymmetric addition reactions: a) addition of indo...
Scheme 15: Bisthiourea catalyzed oxa-Pictet–Spengler reaction of indole-based alcohols and aromatic aldehydes ...
Scheme 16: Anion-binding catalyst development in the enantioselective addition of silyl ketene acetals to 1-ch...
Scheme 17: a) Macrocyclic bis-thiourea catalyst in a diastereoselective glycosylation reaction. b) Competing SN...
Scheme 18: a) Folding mechanism of oligotriazoles upon anion recognition. b) Representative tetratriazole 82 c...
Scheme 19: Switchable chiral tetratriazole catalyst 86 in the enantioselective addition of silyl ketene acetal...
Influence of the cis/trans configuration on the supramolecular aggregation of aryltriazoles
- Sara Tejera,
- Giada Caniglia,
- Rosa L. Dorta,
- Andrea Favero,
- Javier González-Platas and
- Jesús T. Vázquez
Beilstein J. Org. Chem. 2019, 15, 2881–2888, doi:10.3762/bjoc.15.282
- (10), forming gels much easier than their corresponding β-anomers (trans). This showed that their ability to form gels was critically dependent on the cis/trans configuration present in the molecule. To confirm this result, the supramolecular properties of trans- and cis-1,2-bis(4-(4-bromophenyl)-1H
Graphical Abstract
Scheme 1: Structures of 4-substituted 1-glucopyranosyltriazoles 1a–g and 2a–g [15].
Scheme 2: Synthesis of 1,2-cis-/trans-bistriazoles 7a–7g and 8a–8g [15].
Scheme 3: Compounds 9 (trans) and 10 (cis) [15].
Scheme 4: Synthesis of (1R,2R)- and (1R,2S)-1,2-bis-(4-(4-bromophenyl)-1H-triazol-1-yl)cyclohexane (12 and 14...
Figure 1: Tube inversion test: gels formed by compounds 7f, 8f, 10, 12, and 14.
Figure 2: SEM images of the xerogels of compounds 7f (DMSO, top left), 8f (DMSO/H2O, 3:1, v/v, top right), 10...
Figure 3: ORTEP representation of the molecular structure of compound 12 (trans configuration) obtained from ...
Figure 4: Crystal packing of compound 12 (trans configuration) in DMSO.
Figure 5: Crystal packing of 10 (cis configuration) in DMSO/H2O (1:1, v/v). Colored lines: π–π stacking inter...
Figure 6: CD spectra of compound 10 (cis) in DMSO/H2O (1:2, v/v) in solution (in black) and as gel (in blue).
Molecular recognition using tetralactam macrocycles with parallel aromatic sidewalls
- Dong-Hao Li and
- Bradley D. Smith
Beilstein J. Org. Chem. 2019, 15, 1086–1095, doi:10.3762/bjoc.15.105
- Dong-Hao Li Bradley D. Smith Department of Chemistry and Biochemistry, University of Notre Dame, 236 Nieuwland Science Hall, Notre Dame, Indiana 46556, United States 10.3762/bjoc.15.105 Abstract This review summarizes the supramolecular properties of tetralactam macrocycles that have parallel
Graphical Abstract
Scheme 1: Chemical structures of the tetralactam host macrocycles that are covered by this review.
Figure 1: X-ray crystal structures of various squaraine rotaxanes show that the macrocycle bridging units con...
Figure 2: X-ray crystal structures of macrocycles that are representative of the tetralactam systems in Scheme 1. In ...
Scheme 2: Synthetic yields of [2]rotaxanes with different dumbbell-shaped templates and tetralactam A as the ...
Scheme 3: Supramolecular picture of the amide-bond-formation step that clips tetralactam A around a biscarbon...
Figure 3: Selected X-ray structures of [2]rotaxanes with tetralactam A as the surrounding macrocycle reported...
Figure 4: (a) Chemical structures of squaraine, thiosquaraine, croconaine, and acene guests that can bind ins...
Scheme 4: Complex stabilization due to guest back folding and aromatic stacking with the surrounding tetralac...
Figure 5: (a) Shape and electrostatic comparison of squaraine C4O2 core (left) with anionic square planar met...
Figure 6: Chemical structures of a) acetylcholine chloride, 26+·Cl−, (b) trimethyl-p-cyanobenzylammonium chlo...
Figure 7: a) Chemical structure of β-D-glucopyranose and the solid-state structure of its complexes with macr...
Calixazulenes: azulene-based calixarene analogues – an overview and recent supramolecular complexation studies
- Paris E. Georghiou,
- Shofiur Rahman,
- Abdullah Alodhayb,
- Hidetaka Nishimura,
- Jaehyun Lee,
- Atsushi Wakamiya and
- Lawrence T. Scott
Beilstein J. Org. Chem. 2018, 14, 2488–2494, doi:10.3762/bjoc.14.225
- -hydrocarbon calix[4]azulenes which have been synthesized in good yields by their method. This allowed studying their supramolecular properties. This report is of our latest work on the solution-state supramolecular complexation of one of these calix[4]azulenes, namely tetrakis(5,7-diphenyl)calix[4]azulene or
- solvents prevented a fuller examination of its potential supramolecular properties with fullerenes, a topic of particular interest to us [18]. Therefore, the solid state supramolecular complexation properties of 5 were experimentally studied using solid state NMR and XRD experiments, and also theoretically
- , using a DFT analysis [17]. We previously used a similar solid-state NMR approach to study the solid-state supramolecular properties of tetra-6-tert-butylcalix[4]azulene (4) [19]. Unlike these two studies, however, in our first study on calixazulenes which we reported in 2015, we were able to demonstrate
Graphical Abstract
Figure 1: Examples of calix[n]arenes 1 and calix[4]azulenes 2–5.
Figure 2: Three major computed conformers of OPC4A; a: 1,2-alternate; b: cone and c: saddle.
Figure 3: Geometry-optimized (ωB97xD/6-31G(d)) and (ωB97xD/GenECP) structures, respectively, computed for lef...
Dynamic light scattering studies of the effects of salts on the diffusivity of cationic and anionic cavitands
- Anthony Wishard and
- Bruce C. Gibb
Beilstein J. Org. Chem. 2018, 14, 2212–2219, doi:10.3762/bjoc.14.195
- [4][10][11]. Although many attempts have been made to amend these and other classical models [4], success has been limited because of our lack of understanding of the specific supramolecular properties of individual ions. There is therefore an opportunity for supramolecular chemists (who by their
Graphical Abstract
Figure 1: Chemical structures of octaacid 1 and positand 2 showing the anionic binding sites of the two hosts...
Figure 2: Representative plots of the volume-weighted distribution obtained by DLS for salts titrated into 2....
Figure 3: Representative plots of the volume-weighted distribution obtained by DLS for salts titrated into 2....
Scheme 1: Visualization of the competitive equilibrium between iodide binding to host 2 or associating with i...
Synthesis and supramolecular properties of regioisomers of mononaphthylallyl derivatives of γ-cyclodextrin
- Markéta Bláhová,
- Sergey K. Filippov,
- Lubomír Kováčik,
- Jiří Horský,
- Simona Hybelbauerová,
- Zdenka Syrová,
- Tomáš Křížek and
- Jindřich Jindřich
Beilstein J. Org. Chem. 2017, 13, 2509–2520, doi:10.3762/bjoc.13.248
- -(naphthalen-2-yl)allyl chloride as the alkylating reagent. Highly regioselective reaction conditions, which differ for each regioisomer in a used base, gave the monosubstituted isomers in yields between 12–19%. Supramolecular properties of these derivatives were studied by DLS, ITC, NMR, and Cryo-TEM
- . Keywords: γ-cyclodextrin; naphthylallyl derivatives; regioselective alkylation; supramolecular properties; synthesis; Introduction Cyclodextrins [1] (CDs) are cyclic oligosaccharides with a cone-shaped cavity formed by α-1,4-linked D-glucopyranose units. The most widely used CDs are α-, β-, and γ-CD with
- polymers of CD–guest type [17]. Moreover, the double bond of the allyl group allows a subsequent conversion of these compounds to other regiospecifically monosubstituted γ-CD derivatives. Naphthylallyl derivatives of any CD have not been described yet. Supramolecular properties of the prepared derivatives
Graphical Abstract
Scheme 1: Preparation of 2I-O-, 3I-O- and 6I-O-naphthylallyl derivatives of γ-CD by cross-metathesis.
Scheme 2: Preparation of 2-O-, 3-O- and 6-O-NA derivatives of γ-CD by direct alkylation (see Table 1 for the yields ...
Figure 1: Volume-weighted distribution functions for water solutions of 2-O- (2a), 3-O- (2b), and 6-O- (2c) N...
Figure 2: Distribution functions for 2-O- (2a), 3-O- (2b), and 6-O- (2c) NA-γ-CD regioisomers in 50% MeOH (v/...
Figure 3: Volume-weighted distribution functions for the 3-O- (2b) and 6-O- (2c) NA-γ-CD regioisomer at diffe...
Figure 4: Effect of increasing concentration and sonication on the morphology of the 3-O-derivative 2b. A to ...
Figure 5: Effect of increasing concentration and sonication on the morphology of the 2-O-derivative 2a. A: 2 ...
Figure 6: Effect of increasing concentration and sonication on the morphology of the 6-O-derivative 2c. A: 0....
Figure 7: Heat change for injection per mole of NA-γ-CD added as a function of the total concentration of NA-...
Figure 8: 1H NMR spectra of 2-O-derivative 2a in D2O at concentrations of 100, 10, and 1 mM.
Figure 9: 1H NMR spectra of 3-O-derivative 2b in D2O at concentrations of 100, 10, and 1 mM.
Figure 10: Putative objects and interactions in naphthylallyl-γ-CD solution, depicted schematically for 6I-O-n...
Phosphonic acid: preparation and applications
- Charlotte M. Sevrain,
- Mathieu Berchel,
- Hélène Couthon and
- Paul-Alain Jaffrès
Beilstein J. Org. Chem. 2017, 13, 2186–2213, doi:10.3762/bjoc.13.219
- oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for
- incorporated in a broad diversity of molecules and polymers to introduce specific properties including water solubility, coordination or supramolecular properties. Several books, book chapters or reviews have been focused on the construction of the P–C bond [1], on the description of the different classes of
Graphical Abstract
Figure 1: Summary of the synthetic routes to prepare phosphonic acids detailed in this review. The numbers in...
Figure 2: Chemical structure of dialkyl phosphonate, phosphonic acid and illustration of the simplest phospho...
Figure 3: Illustration of some phosphonic acid exhibiting bioactive properties. A) Phosphonic acids for biome...
Figure 4: Illustration of the use of phosphonic acids for their coordination properties and their ability to ...
Figure 5: Hydrolysis of dialkyl phosphonate to phosphonic acid under acidic conditions.
Figure 6: Examples of phosphonic acids prepared by hydrolysis of dialkylphosphonate with HCl 35% at reflux (16...
Figure 7: A) and B) Observation of P–C bond breaking during the hydrolysis of phosphonate with concentrated H...
Figure 8: Mechanism of the hydrolysis of dialkyl phosphonate with HCl in water.
Figure 9: Hydrolysis of bis-tert-butyl phosphonate 28 into phosphonic acid 29 [137].
Figure 10: A) Hydrolysis of diphenyl phosphonate into phosphonic acid in acidic media. B) Examples of phosphon...
Figure 11: Suggested mechanism occurring for the first step of the hydrolysis of diphenyl phosphonate into pho...
Figure 12: A) Hydrogenolysis of dibenzyl phosphonate to phosphonic acid. B) Compounds 33, 34 and 35 were prepa...
Figure 13: A) Preparation of phosphonic acid from diphenyl phosphonate with the Adam’s catalyst. B) Compounds ...
Figure 14: Suggested mechanism for the preparation of phosphonic acid from dialkyl phosphonate using bromotrim...
Figure 15: A) Reaction of the phosphonate-thiophosphonate 37 with iodotrimethylsilane followed by methanolysis...
Figure 16: Synthesis of hydroxymethylenebisphosphonic acid by reaction of tris(trimethylsilyl) phosphite with ...
Figure 17: Synthesis of the phosphonic acid disodium salt 48 by reaction of mono-hydrolysed phosphonate 47 wit...
Figure 18: Phosphonic acid synthesized by the sequence 1) bromotrimethylsilane 2) methanolysis or hydrolysis. ...
Figure 19: Polyphosphonic acids and macromolecular compounds prepared by the hydrolysis of dialkyl phosphonate...
Figure 20: Examples of organometallic complexes functionalized with phosphonic acids that were prepared by the...
Figure 21: Side reaction observed during the hydrolysis of methacrylate monomer functionalized with phosphonic...
Figure 22: Influence of the reaction time during the hydrolysis of compound 76.
Figure 23: Dealkylation of dialkyl phosphonates with boron tribromide.
Figure 24: Dealkylation of diethylphosphonate 81 with TMS-OTf.
Figure 25: Synthesis of substituted phenylphosphonic acid 85 from the phenyldichlorophosphine 83.
Figure 26: Hydrolysis of substituted phenyldichlorophosphine oxide 86 under basic conditions.
Figure 27: A) Illustration of the synthesis of chiral phosphonic acids from phosphonodiamides. B) Examples of ...
Figure 28: A) Illustration of the synthesis of the phosphonic acid 98 from phosphonodiamide 97. B) Use of cycl...
Figure 29: Synthesis of tris(phosphonophenyl)phosphine 109.
Figure 30: Moedritzer–Irani reaction starting from A) primary amine or B) secondary amine. C) Examples of phos...
Figure 31: Phosphonic acid-functionalized polymers prepared by Moedritzer–Irani reaction.
Figure 32: Reaction of phosphorous acid with imine in the absence of solvent.
Figure 33: A) Reaction of phosphorous acid with nitrile and examples of aminomethylene bis-phosphonic acids. B...
Figure 34: Reaction of carboxylic acid with phosphorous acid and examples of compounds prepared by this way.
Figure 35: Synthesis of phosphonic acid by oxidation of phosphinic acid (also identified as phosphonous acid).
Figure 36: Selection of reaction conditions to prepare phosphonic acids from phosphinic acids.
Figure 37: Synthesis of phosphonic acid from carboxylic acid and white phosphorus.
Figure 38: Synthesis of benzylphosphonic acid 136 from benzaldehyde and red phosphorus.
Figure 39: Synthesis of graphene phosphonic acid 137 from graphite and red phosphorus.
Bi- and trinuclear copper(I) complexes of 1,2,3-triazole-tethered NHC ligands: synthesis, structure, and catalytic properties
- Shaojin Gu,
- Jiehao Du,
- Jingjing Huang,
- Huan Xia,
- Ling Yang,
- Weilin Xu and
- Chunxin Lu
Beilstein J. Org. Chem. 2016, 12, 863–873, doi:10.3762/bjoc.12.85
- range of 157.6–216 ppm [34][35]. Single crystal X-ray diffraction studies To obtain additional insight into the coordination and supramolecular properties, suitable single crystals of all the copper complexes were obtained for single-crystal X-ray diffraction analysis. Crystals were grown by slow
Graphical Abstract
Scheme 1: Synthesis of copper complexes 2–6.
Figure 1: X-ray diffraction structure of copper(II) complex 2 with thermal ellipsoids drawn at 30% probabilit...
Figure 2: ORTEP the cationic section of [Cu2(L2)2](PF6)2 (3). Thermal ellipsoids are drawn at the 30% probabi...
Figure 3: ORTEP drawing of [Cu2(L3)2](PF6)2 (4). Thermal ellipsoids are drawn at the 30% probability level. H...
Figure 4: ORTEP drawing of [Cu3(L4)3](PF6)3 (5). Thermal ellipsoids are drawn at the 30% probability level. H...
Figure 5: ORTEP drawing of [Cu3(L5)3](PF6)3 (6). Thermal ellipsoids are drawn at the 30% probability level. H...
Figure 6: Yield vs reaction time of different copper complex. The reaction was carried out in acetonitrile-d3...
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
- the supramolecular properties of the CD and the coordination ability of the phosphane were combined into the same molecular object. During the course of the reaction, the closeness of the three main protagonists (substrate, CD, phosphane) led to a significant increase in the conversion compared to a
Graphical Abstract
Scheme 1: Synthesis of CD-substituted polymers 3a, 3b and 3c.
Figure 1: 1H NMR spectrum of 3c in D2O at 25 °C.
Figure 2: 31P NMR spectrum of 3b in a) DMF-d7 at 25 °C and b) D2O at 25 °C.
Figure 3: 1H NMR spectrum of 3b (10 mM) in D2O at 25 °C (below) and 60 °C (above).
Figure 4: Size-exclusion chromatography of polyNAS and polymers 3a, 3b and 3c.
Cyclodextrin-based nanosponges as drug carriers
- Francesco Trotta,
- Marco Zanetti and
- Roberta Cavalli
Beilstein J. Org. Chem. 2012, 8, 2091–2099, doi:10.3762/bjoc.8.235
- nanoscale structural characteristics can be expected to provide many potential applications in the field of nanomedicine. Cyclodextrins [1][2][3] are nanometric biomaterials with a close relationship between molecular status and supramolecular properties. They are a class of cyclic glucopyranose oligomers
Graphical Abstract
Scheme 1: Synthetic routes to cyclodextrin nanosponges. (a) Cyclodextrin carbonate nanosponges. (b) Cyclodext...
Figure 1: Molecular structure of cyclodextrin carbonate nanosponges.
Figure 2: TEM microphotograph of cyclodextrin carbonate nanosponge (magnification 46,000×).
Low-generation dendrimers with a calixarene core and based on a chiral C2-symmetric pyrrolidine as iminosugar mimics
- Marco Marradi,
- Stefano Cicchi,
- Francesco Sansone,
- Alessandro Casnati and
- Andrea Goti
Beilstein J. Org. Chem. 2012, 8, 951–957, doi:10.3762/bjoc.8.107
- rigidification of the dendrimer structure and the iminosugar presentation in the clusters. The combination of the supramolecular properties of calixarenes with the advantage of a dendrimeric presentation of repetitive units opens up the possibility of generating well-defined multivalent and multifaceted systems
- for a significant multivalent effect in glycosidase inhibition. These results highlight the interest in synthesizing multivalent iminosugar-conjugates with well-defined structures. In this context, we aimed at studying the feasibility of combining the supramolecular properties of multivalent scaffolds
Graphical Abstract
Figure 1: First (2) and second (3) generation of dendrimers based on chiral C2-symmetric pyrrolidine 1 and ha...
Scheme 1: Use of the key intermediate (3S,4S)-1-benzyl-3,4-dihydroxypyrrolidine (6) [31] for the synthesis of pyr...
Scheme 2: Synthesis of calixarene-based dendrimers 2 and 3. Reagents and conditions: DIPEA, CH2Cl2, 30 °C, 5 ...
Figure 2: Expansion (about 7 to 3 ppm) of the 1H NMR spectra of (A) the free ligand 2, (B) the sodium picrate...
Figure 3: Schematic of the inclusion of alkali-metal ions (sodium and potassium) in the polar cavity defined ...
Molecular recognition of organic ammonium ions in solution using synthetic receptors
- Andreas Späth and
- Burkhard König
Beilstein J. Org. Chem. 2010, 6, No. 32, doi:10.3762/bjoc.6.32
Graphical Abstract
Figure 1: Biologically important amines and quaternary ammonium salts: histamine (1), dopamine (2) and acetyl...
Figure 2: Crown ether 18-crown-6.
Figure 3: Conformations of 18-crown-6 (4) in solvents of different polarity.
Figure 4: Binding topologies of the ammonium ion depending on the crown ring size.
Figure 5: A “pseudorotaxane” structure consisting of 24-crown-8 and a secondary ammonium ion (5); R = Ph.
Figure 6: Typical examples of azacrown ethers, cryptands and related aza macrocycles.
Figure 7: Binding of ammonium to azacrown ethers and cryptands [111-113].
Figure 8: A 19-crown-6-ether with decalino blocking groups (11) and a thiazole-dibenzo-18-crown-6-ether (12).
Figure 9: 1,3-Bis(6-oxopyridazin-1-yl)propane derivatives 13 and 14 by Campayo et al.
Figure 10: Fluorescent azacrown-PET-sensors based on coumarin.
Figure 11: Two different pyridino-cryptands (17 and 18) compared to a pyridino-crown (19); chiral ammonium ion...
Figure 12: Pyridino-18-crown-6 ligand (21), a similar acridino-18-crown-6 ligand (22) and a structurally relat...
Figure 13: Ciral pyridine-azacrown ether receptors 24.
Figure 14: Chiral 15-crown-5 receptors 26 and an analogue 18-crown-6 ligand 27 derived from amino alcohols.
Figure 15: C2-symmetric chiral 18-crown-6 amino alcohol derivatives 28 and related macrocycles.
Figure 16: Macrocycles with diamide-diester groups (30).
Figure 17: C2-symmetric chiral aza-18-crown-6 ethers (31) with phenethylamine residues.
Figure 18: Chiral C-pivot p-methoxy-phenoxy-lariat ethers.
Figure 19: Chiral lariat crown ether 34.
Figure 20: Sucrose-based chiral crown ether receptors 36.
Figure 21: Permethylated fructooligosaccharide 37 showing induced-fit chiral recognition.
Figure 22: Biphenanthryl-18-crown-6 derivative 38.
Figure 23: Chiral lariat crown ethers derived from binol by Fuji et al.
Figure 24: Chiral phenolic crown ether 41 with “aryl chiral barriers” and guest amines.
Figure 25: Chiral bis-crown receptor 43 with a meso-ternaphthalene backbone.
Figure 26: Chromogenic pH-dependent bis-crown chemosensor 44 for diamines.
Figure 27: Triamine guests for binding to receptor 44.
Figure 28: Chiral bis-crown phenolphthalein chemosensors 46.
Figure 29: Crown ether amino acid 47.
Figure 30: Luminescent receptor 48 for bis-alkylammonium guests.
Figure 31: Luminescent CEAA (49a), a bis-CEAA receptor for amino acids (49b) and the structure of lysine bindi...
Figure 32: Luminescent CEAA tripeptide for binding small peptides.
Figure 33: Bis crown ether 51a self assembles co-operatively with C60-ammonium ion 51b.
Figure 34: Triptycene-based macrotricyclic dibenzo-[24]-crown-8 ether host 52 and guests.
Figure 35: Copper imido diacetic acid azacrown receptor 53a and the suggested His-Lys binding motif; a copper ...
Figure 36: Urea (54) and thiourea (55) benzo crown receptor for transport and extraction of amino acids.
Figure 37: Crown pyryliums ion receptors 56 for amino acids.
Figure 38: Ditopic sulfonamide bridged crown ether receptor 57.
Figure 39: Luminescent peptide receptor 58.
Figure 40: Luminescent receptor 59 for the detection of D-glucosamine hydrochloride in water/ethanol and lumin...
Figure 41: Guanidinium azacrown receptor 61 for simple amino acids and ditopic receptor 62 with crown ether an...
Figure 42: Chiral bicyclic guanidinium azacrown receptor 63 and similar receptor 64 for the enantioselective t...
Figure 43: Receptors for zwitterionic species based on luminescent CEAAs.
Figure 44: 1,10-Azacrown ethers with sugar podand arms and the anticancer agent busulfan.
Figure 45: Benzo-18-crown-6 modified β-cyclodextrin 69 and β-cyclodextrin functionalized with diaza-18-crown-6...
Figure 46: Receptors for colorimetric detection of primary and secondary ammonium ions.
Figure 47: Porphyrine-crown-receptors 72.
Figure 48: Porphyrin-crown ether conjugate 73 and fullerene-ammonium ion guest 74.
Figure 49: Calix[4]arene (75a), homooxocalix[4]arene (75b) and resorcin[4]arene (75c) compared (R = H, alkyl c...
Figure 50: Calix[4]arene and ammonium ion guest (R = H, alkyl, OAcyl etc.), possible binding sites; A: co-ordi...
Figure 51: Typical guests for studies with calixarenes and related molecules.
Figure 52: Lower rim modified p-tert-butylcalix[5]arenes 82.
Figure 53: The first example of a water soluble calixarene.
Figure 54: Sulfonated water soluble calix[n]arenes that bind ammonium ions.
Figure 55: Displacement assay for acetylcholine (3) with a sulfonato-calix[6]arene (84b).
Figure 56: Amino acid inclusion in p-sulfonatocalix[4]arene (84a).
Figure 57: Calixarene receptor family 86 with upper and lower rim functionalization.
Figure 58: Calix[6]arenes 87 with one carboxylic acid functionality.
Figure 59: Sulfonated calix[n]arenes with mono-substitution at the lower rim systematically studied on their r...
Figure 60: Cyclotetrachromotropylene host (91) and its binding to lysine (81c).
Figure 61: Calixarenes 92 and 93 with phosphonic acids groups.
Figure 62: Calix[4]arene tetraphosphonic acid (94a) and a double bridged analogue (94b).
Figure 63: Calix[4]arene tetraphosphonic acid ester (92c) for surface recognition experiments.
Figure 64: Calixarene receptors 95 with α-aminophosphonate groups.
Figure 65: A bridged homocalix[3]arene 95 and a distally bridged homocalix[4]crown 96.
Figure 66: Homocalix[3]arene ammonium ion receptor 97a and the Reichardt’s dye (97b) for colorimetric assays.
Figure 67: Chromogenic diazo-bridged calix[4]arene 98.
Figure 68: Calixarene receptor 99 by Huang et al.
Figure 69: Calixarenes 100 reported by Parisi et al.
Figure 70: Guest molecules for inclusion in calixarenes 100: DAP × 2 HCl (101a), APA (101b) and Lys-OMe × 2 HC...
Figure 71: Different N-linked peptido-calixarenes open and with glycol chain bridges.
Figure 72: (S)-1,1′-Bi-2-naphthol calixarene derivative 104 published by Kubo et al.
Figure 73: A chiral ammonium-ion receptor 105 based on the calix[4]arene skeleton.
Figure 74: R-/S-phenylalaninol functionalized calix[6]arenes 106a and 106b.
Figure 75: Capped homocalix[3]arene ammonium ion receptor 107.
Figure 76: Two C3 symmetric capped calix[6]arenes 108 and 109.
Figure 77: Phosphorous-containing rigidified calix[6]arene 110.
Figure 78: Calix[6]azacryptand 111.
Figure 79: Further substituted calix[6]azacryptands 112.
Figure 80: Resorcin[4]arene (75c) and the cavitands (113).
Figure 81: Tetrasulfonatomethylcalix[4]resorcinarene (114).
Figure 82: Resorcin[4]arenes (115a/b) and pyrogallo[4]arenes (115c, 116).
Figure 83: Displacement assay for acetylcholine (3) with tetracyanoresorcin[4]arene (117).
Figure 84: Tetramethoxy resorcinarene mono-crown-5 (118).
Figure 85: Components of a resorcinarene based displacement assay for ammonium ions.
Figure 86: Chiral basket resorcin[4]arenas 121.
Figure 87: Resorcinarenes with deeper cavitand structure (122).
Figure 88: Resorcinarene with partially open deeper cavitand structure (123).
Figure 89: Water-stabilized deep cavitands with partially structure (124, 125).
Figure 90: Charged cavitands 126 for tetralkylammonium ions.
Figure 91: Ditopic calix[4]arene receptor 127 capped with glycol chains.
Figure 92: A calix[5]arene dimer for diammonium salt recognition.
Figure 93: Calixarene parts 92c and 129 for the formation molecular capsules.
Figure 94: Encapsulation of a quaternary ammonium cation by two resorcin[4]arene molecules (NMe4+@[75c]2 × Cl−...
Figure 95: Encapsulation of a quaternary ammonium cation by six resorcin[4]arene molecules (NMe3D+@[130]6 × Cl−...
Figure 96: Structure and schematic of cucurbit[6]uril (CB[6], 131a).
Figure 97: Cyclohexanocucurbit[6]uril (CB′[6], 132) and the guest molecule spermine (133).
Figure 98: α,α,δ,δ-Tetramethylcucurbit[6]uril (134).
Figure 99: Structure of the cucurbituril-phthalhydrazide analogue 135.
Figure 100: Organic cavities for the displacement assay for amine differentiation.
Figure 101: Displacement assay methodology for diammonium- and related guests involving cucurbiturils and some ...
Figure 102: Nor-seco-Cucurbituril (±)-bis-ns-CB[6] (140) and guest molecules.
Figure 103: The cucurbit[6]uril based complexes 141 for chiral discrimination.
Figure 104: Cucurbit[7]uril (131c) and its ferrocene guests (142) opposed.
Figure 105: Cucurbit[7]uril (131c) guest inclusion and representative guests.
Figure 106: Cucurbit[7]uril (131c) binding to succinylcholine (145) and different bis-ammonium and bis-phosphon...
Figure 107: Paraquat-cucurbit[8]uril complex 149.
Figure 108: Gluconuril-based ammonium receptors 150.
Figure 109: Examples of clefts (151a), tweezers (151b, 151c, 151d) and clips (151e).
Figure 110: Kemp’s triacid (152a), on example of Rebek’s receptors (152b) and guests.
Figure 111: Amino acid receptor (154) by Rebek et al.
Figure 112: Hexagonal lattice designed hosts by Bell et al.
Figure 113: Bell’s amidinium receptor (156) and the amidinium ion (157).
Figure 114: Aromatic phosphonic acids.
Figure 115: Xylene phosphonates 159 and 160a/b for recognition of amines and amino alcohols.
Figure 116: Bisphosphonate recognition motif 161 for a colorimetric assay with alizarin complexone (163) for ca...
Figure 117: Bisphosphonate/phosphate clip 164 and bisphosphonate cleft 165.
Figure 118: N-Methylpyrazine 166a, N-methylnicotinamide iodide (166b) and NAD+ (166c).
Figure 119: Bisphosphate cavitands.
Figure 120: Bisphosphonate 167 of Schrader and Finocchiaro.
Figure 121: Tweezer 168 for noradrenaline (80b).
Figure 122: Different tripods and heparin (170).
Figure 123: Squaramide based receptors 172.
Figure 124: Cage like NH4+ receptor 173 of Kim et al.
Figure 125: Ammonium receptors 174 of Chin et al.
Figure 126: 2-Oxazolin-based ammonium receptors 175a–d and 176 by Ahn et al.
Figure 127: Racemic guest molecules 177.
Figure 128: Tripods based on a imidazole containing macrocycle (178) and the guest molecules employed in the st...
Figure 129: Ammonium ion receptor 180.
Figure 130: Tetraoxa[3.3.3.3]paracyclophanes 181 and a cyclophanic tetraester (182).
Figure 131: Peptidic bridged paraquat-cyclophane.
Figure 132: Shape-selective noradrenaline host.
Figure 133: Receptor 185 for binding of noradrenaline on surface layers from Schrader et al.
Figure 134: Tetraphosphonate receptor for binding of noradrenaline.
Figure 135: Tetraphosphonate 187 of Schrader and Finocchiaro.
Figure 136: Zinc-Porphyrin ammonium-ion receptors 188 and 189 of Mizutani et al.
Figure 137: Zinc porphyrin receptor 190.
Figure 138: Zinc porphyrin receptors 191 capable of amino acid binding.
Figure 139: Zinc-porphyrins with amino acid side chains for stereoinduction.
Figure 140: Bis-zinc-bis-porphyrin based on Tröger’s base 193.
Figure 141: BINAP-zinc-prophyrin derivative 194 and it’s guests.
Figure 142: Bisaryl-linked-zinc-porphyrin receptors.
Figure 143: Bis-zinc-porphyrin 199 for diamine recognition and guests.
Figure 144: Bis-zinc-porphyrin crown ether 201.
Figure 145: Bis-zinc-porphyrin 202 for stereodiscrimination (L = large substituent; S = small substituent).
Figure 146: Bis-zinc-porphyrin[3]rotaxane and its copper complex and guests.
Figure 147: Dien-bipyridyl ligand 206 for co-ordination of two metal atoms.
Figure 148: The ligand and corresponding tetradentate co-complex 207 serving as enantioselective receptor for a...
Figure 149: Bis(oxazoline)–copper(II) complex 208 for the recognition of amino acids in aqueous solution.
Figure 150: Zinc-salen-complexes 209 for the recognition tertiary amines.
Figure 151: Bis(oxazoline)–copper(II) 211 for the recognition of amino acids in aqueous solution.
Figure 152: Zn(II)-complex of a C2 terpyridine crown ether.
Figure 153: Displacement assay and receptor for aspartate over glutamate.
Figure 154: Chiral complex 214 for a colorimetric displacement assay for amino acids.
Figure 155: Metal complex receptor 215 with tripeptide side arms.
Figure 156: A sandwich complex 216 and its displaceable dye 217.
Figure 157: Lanthanide complexes 218–220 for amino acid recognition.
Figure 158: Nonactin (221), valinomycin (222) and vancomycin (223).
Figure 159: Monesin (224a) and a chiral analogue for enantiodiscrimination of ammonium guests (224b).
Figure 160: Chiral podands (226) compared to pentaglyme-dimethylether (225) and 18-crown-6 (4).
Figure 161: Lasalocid A (228).
Figure 162: Lasalocid derivatives (230) of Sessler et al.
Figure 163: The Coporphyrin I tetraanion (231).
Figure 164: Linear and cyclic peptides for ammonium ion recognition.
Figure 165: Cyclic and bicyclic depsipeptides for ammonium ion recognition.
Figure 166: α-Cyclodextrin (136a) and novocaine (236).
Figure 167: Helical diol receptor 237 by Reetz and Sostmann.
Figure 168: Ammonium binding spherand by Cram et al. (238a) and the cyclic[6]metaphenylacetylene 238b in compar...
Figure 169: Receptor for peptide backbone and ammonium binding (239).
Figure 170: Anion sensor principle with 3-hydroxy-2-naphthanilide of Jiang et al.
Figure 171: 7-bromo-3-hydroxy-N-(2-hydroxyphenyl)naphthalene 2-carboxamide (241) and its amine binding.
Figure 172: Naturally occurring catechins with affinity to quaternary ammonium ions.
Figure 173: Spiropyran (244) and merocyanine form (244a) of the amino acid receptors of Fuji et al.
Figure 174: Coumarin aldehyde (245) and its iminium species with amino acid bound (245a) by Glass et al.
Figure 175: Coumarin aldehyde appended with boronic acid.
Figure 176: Quinolone aldehyde dimers by Glass et al.
Figure 177: Chromogenic ammonium ion receptors with trifluoroacetophenone recognition motifs.
Figure 178: Chromogenic ammonium ion receptor with trifluoroacetophenone recognition motif bound on different m...
(Pseudo)amide-linked oligosaccharide mimetics: molecular recognition and supramolecular properties
- José L. Jiménez Blanco,
- Fernando Ortega-Caballero,
- Carmen Ortiz Mellet and
- José M. García Fernández
Beilstein J. Org. Chem. 2010, 6, No. 20, doi:10.3762/bjoc.6.20
- phosphate were obtained from NMR titration experiments for both series of glucooligomers. The binding affinity of the thiourea and guanidine oligomers was stronger than in the case of the urea analogues. Stimulated by the interesting supramolecular properties and applications of cyclodextrins (CDs), a range
Graphical Abstract
Figure 1: Schematic representation of sugar aminoacids (SAAs) and (pseudo)amide oligosaccharide mimetics.
Figure 2: Natural SAAs structures and natural nucleosidic antibiotics.
Scheme 1: Synthetic route to the target amide-linked sialooligomers. (a) Fmoc-Cl, NaHCO3, H2O, dioxane, 0 °C....
Figure 3: The general structure of glycoamino acids and their corresponding oligomers.
Figure 4: Conformational analysis of the β(1→2)-amide-linked glucooligomer 9.
Figure 5: Short oligomeric chains of C-glycosyl D-arabino THF amino acid oligomers.
Figure 6: (A) Stereoview of the minimized structure of compound 16 (produced by a 500 ps simulation) that mos...
Figure 7: Structures of linear oxetane-β- and δ-SAA homo-oligomers 19–20.
Figure 8: 10-Membered ring H-bonds in compound 21 consistent with NMR and modelling investigations.
Figure 9: General structure of carbopeptoid-oligonucleotide conjugates.
Figure 10: Protected derivatives of 2,6-diamino-2,6-dideoxy-β-D-glucopyranosyl carboxylic acid 22 and 23.
Figure 11: Cyclic homo-oligomers containing glucopyranoid-SAAs.
Scheme 2: Strategy for solid-phase synthesis of cyclic trimers and tetramers containing pyranoid δ-SAAs.
Figure 12: Cyclic tetramers of L-rhamno- and D-gulo-configured oxetane-SAAs.
Figure 13: Aminoglycosidic antibiotics of the glycocinnamoylspermidine family.
Scheme 3: Synthesis of (thio)trehazoline, via triflate, from β-hydroxy(thio)urea.
Figure 14: Approaches to access pseudoamide-type oligosaccharide mimics.
Figure 15: Calystegine B2 analogues 38 and 39 with urea-linked disaccharide structure.
Figure 16: Rotameric equilibrium shift of 40 by formation of a bidentate hydrogen bond.
Figure 17: Nucleotide analogues with thiourea and S-methylisothiouronium linkers.
Scheme 4: Retrosynthetic approach to synthesize thiourea-linked glycooligomers.
Figure 18: Rotameric equilibria for β-(1→6)-thiourea-linked glucodimer 41.
Figure 19: Schematic representation of (a) cyclodextrin (CDs) and (b) cyclotrehalan (CTs) family members.
Scheme 5: Synthesis of guanidine-linked pseudodisaccharides via carbodiimide.
Figure 20: β(1→6)-Guanidine-linked pseudodi- and pseudotrisaccharides 47 and 48.
Scheme 6: Synthesis of N-benzylguanidine-linked CT2 50.
Figure 21: Structure of RNG and DNG.
Figure 22: Preparation of Fmoc-guanidinium derivatives.
Figure 23: Structures of the homo-oligomeric RNG derivatives 51–55.
Figure 24: Phosphoramidite building block 56.
Figure 25: Structures of DNGs 57–65.
Figure 26: Structure of the phosphoramidite building block 66.
