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Search for "alkali metal" in Full Text gives 60 result(s) in Beilstein Journal of Organic Chemistry.
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
- of a considerable number of iminosugar-like moieties in a reduced volume and in a well-defined geometry. The inclusion of alkali-metal ions (sodium and potassium) in the polar cavity defined by the acetamide moieties at the lower rim of the calixarene was demonstrated, which allows also the
- water. The presence of acetamide moieties at the lower rim of the dendrimers 2 and 3 prompted us to explore the possibility to use alkali metal salts as allosteric effectors in the modulation of the shape and rigidity of the iminosugar presentation by the calixarene scaffold. A common way, in fact, used
- to rigidify the “mobile cone” structure of tetraalkoxycalix[4]arenes is to introduce strong donating groups, such as amide or ester [32][33], on the phenolic oxygen atoms and an alkali-metal ion. The cation, strongly coordinated by eight oxygen atoms in the polar region created at the lower rim
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 ...
Discovery of practical production processes for arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides): Beginning of a new era of “super-trifluoromethyl” arene chemistry and its industry
- Teruo Umemoto,
- Lloyd M. Garrick and
- Norimichi Saito
Beilstein J. Org. Chem. 2012, 8, 461–471, doi:10.3762/bjoc.8.53
- an alkali metal fluoride, and (step 2) treatment of the resulting arylsulfur chlorotetrafluoride with a fluoride source, such as ZnF2, HF, and Sb(III/V) fluorides. The intermediate arylsulfur chlorotetrafluorides were isolated by distillation or recrystallization and characterized. The aspects of
Graphical Abstract
Scheme 1: Preparation of ArSF4Cl 2.
Scheme 2: Preparation of Ar(SF4Cl)n from Ar(SH)n (n = 2, 3).
Scheme 3: Reaction mechanism for the formation of ArSF4Cl.
Scheme 4: Reaction mechanism for the formation of trans and cis-ArSF4Cl.
Scheme 5: Preparation of ArSF5 with ZnF2.
Scheme 6: Preparation of PhSF5 with anhydrous HF.
Scheme 7: Preparation of 3a with HF–pyridine.
Scheme 8: Preparation of polyfluorinated ArSF5.
Scheme 9: Preparation of aryl bis- and tris(sulfur pentafluorides), Ar(SF5)n (n = 2,3).
Fifty years of oxacalix[3]arenes: A review
- Kevin Cottet,
- Paula M. Marcos and
- Peter J. Cragg
Beilstein J. Org. Chem. 2012, 8, 201–226, doi:10.3762/bjoc.8.22
- , derivatives containing carbonyl groups (ester, acid, amide and ketone) and heteroatoms, such as nitrogen and phosphorous, have been obtained. In 1993, Shinkai et al. [29] reported the synthesis of the first ethyl ester derivative 12a. In the belief that the alkali-metal template effect would lead
- -butyl ether 10 derivatives toward alkali-metal cations were estimated by extraction experiments from alkaline aqueous picrate solutions to CH2Cl2 [24], with the latter showing some preference for K+ (59% E) over Na+ (6%) and Cs+ (35%). Replacement of the alkyl groups by residues with additional binding
- was investigated by Masci in 1995 [54] who found that Kassoc values in CDCl3 were modest, ranging from 38 M−1 for N,N,N-trimethylanilinium to 90 M−1 for N,N-dimethylpyrrolidinium, but significantly greater than those of the dihomocalix[4]arene and tetrahomooxacalix[4]arene analogues. 4.1.2 Alkali
Graphical Abstract
Figure 1: Calixarenes and expanded calixarenes: p-tert-Butylcalix[4]arene (1), p-tert-butyldihomooxacalix[4]a...
Figure 2: Conventional nomenclature for oxacalix[n]arenes.
Scheme 1: Synthesis of oxacalix[3]arenes: (i) Formaldehyde (37% aq), NaOH (aq), 1,4-dioxane; glacial acetic a...
Figure 3: p-tert-Butyloctahomotetraoxacalix[4]arene (4a) [16].
Figure 4: X-ray crystal structure of 3a showing phenolic hydrogen bonding (IUCr ID AS0508) [17].
Scheme 2: Stepwise synthesis of asymmetric oxacalix[3]arenes: (i) MOMCl, Adogen®464; (ii) 2,2-dimethoxypropan...
Figure 5: X-ray crystal structure of heptahomotetraoxacalix[3]arene 5 (CCDC ID 166088) [21].
Scheme 3: Oxacalix[3]arene synthesis by reductive coupling: (i) Me3SiOTf, Et3SiH, CH2Cl2; R1, R2 = I, Br, ben...
Scheme 4: Oxacalix[3]naphthalene: (i) HClO4 (aq), wet CHCl3 (R = tert-butyl, 6a, H, 6b) [20].
Figure 6: Conformers of 3a.
Scheme 5: Origin of the 25:75 cone:partial-cone statistical distribution of O-substituted oxacalix[3]arenes (p...
Scheme 6: Synthesis of alkyl ethers 7–10: (i) Alkyl halide, NaH, DMF [24].
Scheme 7: Synthesis of a pyridyl derivative 11a: (i) Picolyl chloride hydrochloride, NaH, DMF [26,27].
Figure 7: X-ray crystal structure of partial-cone 11a (CCDC ID 150580) [26].
Scheme 8: Lower-rim ethyl ester synthesis: (i) Ethyl bromoacetate, NaH, t-BuOK or alkali metal carbonate, THF...
Scheme 9: Forming chiral receptor 13: (i) Ethyl bromoacetate, NaH, THF; (ii) NaOH, H2O/1,4-dioxane; (iii) S-P...
Figure 8: X-ray crystal structure of 16 (IUCr ID PA1110) [32].
Scheme 10: Lower rim N,N-diethylamide 17a: (i) N,N-Diethylchloroacetamide, NaH, t-BuOK or alkali metal carbona...
Scheme 11: Capping the lower rim: (i) N,N-Diethylchloroacetamide, NaH, THF; (ii) NaOH, H2O/1,4-dioxane; (iii) ...
Figure 9: X-ray crystal structure of 18 (CCDC ID 142599) [33].
Scheme 12: Extending the lower rim: (i) Glycine methyl ester, HOBt, dicyclohexycarbodiimide (DCC), CH2Cl2; (ii...
Scheme 13: Synthesis of N-hydroxypyrazinone derivative 23: (i) 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide...
Scheme 14: Synthesis of 24: (i) 1-Adamantyl bromomethyl ketone, NaH, THF [39].
Scheme 15: Synthesis of 25 and 26: (i) (Diphenylphosphino)methyl tosylate, NaH, toluene; (ii) phenylsilane, to...
Figure 10: X-ray crystal structure of 27 in the partial-cone conformer (CCDC ID SUP 90399) [41].
Scheme 16: Synthesis of strapped oxacalix[3]arene derivatives 28 and 29: (i) N,N’-Bis(chloroacetyl)-1,2-ethyle...
Figure 11: A chiral oxacalix[3]arene [45].
Figure 12: X-ray crystal structure of asymmetric oxacalix[3]arene 30 incorporating t-Bu, iPr and Et groups (CC...
Scheme 17: Reactions of an oxacalix[3]arene incorporating an upper-rim Br atom with (i) Pd(OAc)2, PPh3, HCO2H,...
Scheme 18: Synthesis of acid 39: (i) NaOH, EtOH/H2O, HCl (aq) [47].
Figure 13: Two forms of dimeric oxacalix[3]arene 40 [47].
Scheme 19: Capping the upper rim: (i) t-BuLi, THF, −78 °C; (ii) NaBH4, THF/EtOH; (iii) 1,3,5-tris(bromomethyl)...
Figure 14: Oxacalix[3]arene capsules 46 and 47 formed through coordination chemistry [52,53].
Figure 15: X-ray crystal structure of the 3b-vanadyl complex (CCDC ID 240185) [57].
Scheme 20: Effect of Ti(IV)/SiO2 on 3a: (i) Ti(OiPr)4, toluene; (ii) triphenylsilanol, toluene; (iii) partiall...
Figure 16: X-ray crystal structures of oxacalix[3]arene complexes with rhenium: 3b∙Re(CO)3 (CCDC ID 620981, le...
Figure 17: X-ray crystal structure of the La2·3a2 complex (CSD ID TIXXUT) [60].
Figure 18: X-ray crystal structures of [3a∙UO2]− with a cavity-bound cation (CCDC ID 135575, left) and without...
Figure 19: X-ray crystal structure of a supramolecule comprising two [3g·UO2]− complexes that encapsulate a di...
Figure 20: X-ray crystal structure of oxacalix[3]arene 49 capable of chiral selectivity (CSD ID HIGMUF) [65].
Figure 21: The structure of derivative 50 incorporating a Reichardt dye [66].
Figure 22: Phosphorylated oxacalix[3]arene complexes with transition metals: (Left to right) 26∙Au, 26∙Mo(CO)3...
Figure 23: X-ray crystal structure of [17a·HgCl2]2 (CCDC ID 168653) [69].
Figure 24: X-ray crystal structures of 3f with C60 (CCDC ID 182801, left) [76] and a 1,4-bis(9-fluorenyl) C60 deri...
Figure 25: X-Ray crystal structure of 3i and 6a encapsulating C60 (CCDC ID 102473 and 166077) [23,79].
Figure 26: A C60 complexing cationic oxacalix[3]arene 51 [81].
Figure 27: An oxacalix[3]arene-C60 self-associating system 53 [87].
Scheme 21: Synthesis of fluorescent pyrene derivative 55: (i) Propargyl bromide, acetone; (ii) CuI, 1-azidomet...
Scheme 22: Synthesis of responsive rhodamine derivative 57: (i) DCC, CH2Cl2 [91].
Scheme 23: Synthesis of nitrobenzyl derivative 58: (i) 1-Bromo-4-nitrobenzyl acetate, K2CO3, refluxing acetone...
Figure 28: X-ray crystal structure of [Na2∙17a](PF6)2 (CCDC ID 116656) [97].
On the control of secondary carbanion structure utilising ligand effects during directed metallation
- Andrew E. H. Wheatley,
- Jonathan Clayden,
- Ian H. Hillier,
- Alison Campbell Smith,
- Mark A. Vincent,
- Laurence J. Taylor and
- Joanna Haywood
Beilstein J. Org. Chem. 2012, 8, 50–60, doi:10.3762/bjoc.8.5
- authenticated tertiary carbanions, significant similarities are seen insofar as the connectivity of the alkali metal is concerned when changing tridentate Lewis bases. Thus, whereas 6-Lil·PMDTA fails to show a Li–(α-C) interaction in the solid state, in Lil·DGME the corresponding distance (2.406(6) Å) suggests
Graphical Abstract
Scheme 1: Molecular structures of 1/2-H and their corresponding ortho-lithiates [21].
Scheme 2: Molecular structures of 3/4-H and their corresponding lateral lithiates [23,24].
Scheme 3: Conversion of kinetic ortho-lithiate into the thermodynamic lateral lithiate under the influence of...
Scheme 4: Molecular structure of 5-H and its lateral and ortho-lithiates [20].
Scheme 5: Lateral metallation of 6-H using t-BuLi in the presence of Lewis base L.
Figure 1: Molecular structure of 6-Lil·PMDTA; H-atoms (excl. H8) omitted for clarity. Selected bond lengths (...
Scheme 6: Comparison of aromatic and aryl–(α-C) bond distances in 5-Lil·L [20] and 6-Lil·L (L = PMDTA).
Figure 2: Molecular structure of 6-Lil·DGME; H-atoms omitted. Selected bond lengths (Å) and angles (°): O1–Li...
Figure 3: Computed minimum energy conformers (B3LYP density functional/6-311++G(2d,2p) basis set; H-atoms omi...
PEG-embedded KBr3: A recyclable catalyst for multicomponent coupling reaction for the efficient synthesis of functionalized piperidines
- Sanny Verma,
- Suman L. Jain and
- Bir Sain
Beilstein J. Org. Chem. 2011, 7, 1334–1341, doi:10.3762/bjoc.7.157
- alkali metal cations, as shown in Scheme 1. The developed catalyst 3 was readily prepared by the mixing of equimolar amounts of PEG400 (1) and KBr to give [K+PEG]Br− 2, which on subsequent reaction with Br2 resulted in a dark orange-red colored viscous liquid (see Experimental). The liquid was dried
Graphical Abstract
Scheme 1: Synthesis of [K+PEG]Br3−.
Scheme 2: Synthesis of functionalized piperidines.
Figure 1: X-ray structure showing the anti orientation of the phenyl rings at C2 and C6.
Scheme 3: A plausible mechanism for the formation of piperidines.
Combined directed ortho-zincation and palladium-catalyzed strategies: Synthesis of 4,n-dimethoxy-substituted benzo[b]furans
- Verónica Guilarte,
- M. Pilar Castroviejo,
- Estela Álvarez and
- Roberto Sanz
Beilstein J. Org. Chem. 2011, 7, 1255–1260, doi:10.3762/bjoc.7.146
- compounds and different directing groups have been used to facilitate the deprotonation reaction [1][2][3][4][5]. Various strong bases such as alkyl lithiums and their derivatives (for instance, TMEDA-activated complexes [6] and heavier alkali metal tert-butoxide-complexed alkyl lithium reagents, known as
- ), the introduction in the last years of new organometallic “ate” complexes [8][9], which combine an alkali metal with either magnesium, zinc, aluminium, or copper, has allowed more selective metallation reactions. The milder reaction conditions required make these deprotonation reactions tolerant to the
- , as well as of meta-functionalized haloaromatics. In particular, the alkali metal mediated zincation reactions have turned out to be very useful processes and the structures and reaction pathways of TMP-zincates (TMP = 2,2,6,6-tetramethylpiperidine) have been studied in detail [15][16][17][18][19]. On
Graphical Abstract
Figure 1: Some representative dihydroxybenzofuran derived natural products.
Scheme 1: Retrosynthetic analysis of 4,n-dimethoxy-substituted benzo[b]furans.
Scheme 2: Deprotonative zincation of 3-haloanisoles 1.
Meta-metallation of N,N-dimethylaniline: Contrasting direct sodium-mediated zincation with indirect sodiation-dialkylzinc co-complexation
- David R. Armstrong,
- Liam Balloch,
- Eva Hevia,
- Alan R. Kennedy,
- Robert E. Mulvey,
- Charles T. O'Hara and
- Stuart D. Robertson
Beilstein J. Org. Chem. 2011, 7, 1234–1248, doi:10.3762/bjoc.7.144
- -) metallation was favoured by direct sodium-mediated zincation. Keywords: alkali metal; crystal structure; isomerisation; metallation; zincation; Introduction While the metallation reaction remains an essential tool for constructing substituted aromatic compounds [1][2], the quest for new improved reagents
- typically at ambient temperature [11] and on the multi-gram scale with metallation rates comparable to those obtained for small scale processes [12]. Alkali metal zincates have also been given consideration, principally two-component dialkyl-amido zincates MZn(NR2)R′2. The reagent “(LiZn(TMP)(t-Bu)2
- enabled such reagents to perform special metallation reactions that cannot be reproduced by either of the single-metal components that constitute the mixed-metal reagent. While the alkali metal component is essential for the synergic metallation to follow its course, it is the less electropositive zinc
Graphical Abstract
Scheme 1: Proposed stepwise mechanism for the zincation of benzene.
Figure 1: Molecular structure of 2 with selective atom labelling. Hydrogen atoms and minor disorder component...
Scheme 2: Synergic metallation of N,N-dimethylaniline (A) with sodium TMP-zincate 1 to produce 2, which was s...
Figure 2: Molecular structure of 3 with selective atom labelling and thermal ellipsoids drawn at the 50% prob...
Scheme 3: Indirect zincation of N,N-dimethylaniline producing 4, 5 and 6, which was then quenched with I2 to ...
Figure 3: Molecular structure of 4 with selective atom labelling and thermal ellipsoids drawn at the 50% prob...
Figure 4: Solvent-separated ion-pair structure of 5 with selective atom labelling and thermal ellipsoids draw...
Figure 5: Molecular structure of 6 with selective atom labelling and thermal ellipsoids drawn at the 50% prob...
Figure 6: Aromatic region of 1H NMR spectra for deuterated benzene solutions of (a) the crude mixture obtaine...
Figure 7: Relative energy sequence of the four theoretical regioisomers of the experimentally observed produc...
Intramolecular hydroxycarbene C–H-insertion: The curious case of (o-methoxyphenyl)hydroxycarbene
- Dennis Gerbig,
- David Ley,
- Hans Peter Reisenauer and
- Peter R. Schreiner
Beilstein J. Org. Chem. 2010, 6, 1061–1069, doi:10.3762/bjoc.6.121
- was computed to be 262 kcal mol–1, which is comparable to those of alkali metal hydroxides, this seems a viable possibility. Conclusion The formation of a 2,3-dihydrobenzofuran derivative from carbene 5 in the gas phase is the first C–H insertion reaction observed for a hydroxycarbene derivative
Graphical Abstract
Scheme 1: Unimolecular reactivity of hydroxycarbenes under cryogenic conditions: [1,2]H-Tunneling of 1 and 3 (...
Scheme 2: A selection of heterocarbenes that undergo intramolecular C–H insertions.
Scheme 3: Attempted generation of 5 and d-5 as well as their corresponding insertion products.
Scheme 4: Proposed mechanism for the generation of 8 and 9. The [1,2]H-tunneling process apparently cannot co...
Figure 1: Unmodified matrix IR spectrum (Ar, 11 K) of the pyrolysis (600 °C) of 5. Traces of 9 are indicated ...
Figure 2: Unmodified matrix IR spectrum (Ar, 11 K) of the pyrolysis (600 °C) of d-5. Traces of 9 are indicate...
Scheme 5: Decay of the 2,3-dihydrobenzofuran-3-ol molecular radical cation (8+•).
Scheme 6: Attempted generation of 12 and the actual pyrolysis product 11.
Scheme 7: Unanticipated reaction of 6 upon heating in xylenes.
Scheme 8: Potential energy hypersurface of (o-methoxyphenyl)hydroxycarbene (5) (not drawn to scale; ZPVE incl...
Scheme 9: Acid-catalyzed generation of 7 by unreacted 6.
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...
Synthesis and properties of calix[4]arene telluropodant ethers as Ag+ selective sensors and Ag+, Hg2+ extractants
- Yang Lu,
- Yuanyuan Li,
- Song He,
- Yan Lu,
- Changying Liu,
- Xianshun Zeng and
- Langxing Chen
Beilstein J. Org. Chem. 2009, 5, No. 59, doi:10.3762/bjoc.5.59
- selectivity coefficients for Ag+ cations were investigated against alkali metal, alkaline-earth metal, lead, ammonium ions and some transition metal ions using the fixed interference method (FIM) [54][55]. Firstly, the response characteristics of Ag+-ISEs based on different ionophores were tested. It was
Graphical Abstract
Scheme 1: Synthesis and structures of calix[4]arenes 6–8; 3, 6: n = 2; 4, 7: n = 3; 5, 8: n = 5.
Scheme 2: Synthesis of calix[4]arene 10 and 12.
