Search results
Search for "dimeric capsules" in Full Text gives 2 result(s) in Beilstein Journal of Organic Chemistry.
Cone p-aminocalix[4]arenes enriched with ‘clickable’ alkyne or azide functionalities
- Ilia Korniltsev,
- Vasily Bazhenov,
- Alexander Gorbunov,
- Dmitry Cheshkov,
- Stanislav Bezzubov,
- Vladimir Kovalev and
- Ivan Vatsouro
Beilstein J. Org. Chem. 2026, 22, 399–415, doi:10.3762/bjoc.22.28
- virtually any functional units attached to them via triazole groups. Keywords: calixarene amines; dimeric capsules; functionalization; tetraureacalixarenes; triazoles; Introduction Considered generally as multifunctional molecular cores, calixarenes in their native forms as cyclic oligophenols actually
- NMR spectrum of an equimolar mixture of calixarenes 47 and 52 in CDCl3 (Figure 6e). Reasonably, additional non-covalent interactions possibly occurred between two or more calixarene molecules, partially destroying the dimeric capsules and promoting the formation of more complex assemblies, which was
Graphical Abstract
Figure 1: General concept of building multifunctional calix[4]arenes by joining propargyl/2-azidoethyl and p-...
Scheme 1: Silylation of the calixarene propargyl ethers. Conditions: i) LiHMDS (HMDS + n-BuLi), TBSCl, THF, −...
Scheme 2: Nitration of calixarenes 6, 8–10. Conditions: i) HNO3 (fuming, 10 equiv per calixarene aromatic uni...
Figure 2: Parts of 1H,13C HMBC spectra of calixarenes 12 (a) and 13 (b) recorded in CDCl3 solutions at 600 MH...
Figure 3: Molecular structures of partially nitrated calixarene 16 (a) and exhaustively nitrated calixarene 15...
Scheme 3: Reduction of calixarenes 11, 15 and 17. Conditions: i) SnCl2·2H2O, HCl, EtOH, H2O, 70 °C, then KOH,...
Scheme 4: Protecting group replacement in propargylated p-aminocalix[4]arenes. Conditions: i) Boc2O, Et3N, di...
Scheme 5: Synthesis of 2-azidoethylated p-aminocalix[4]arenes. Conditions: i) HNO3 (fuming, 10 equiv per cali...
Scheme 6: Synthesis of triazolated p-aminocalix[4]arenes 37–39 from the propargylated calixarene precursors 24...
Scheme 7: Synthesis of triazolated p-aminocalix[4]arenes 40 and 41 from the 2-azidoethylated calixarene precu...
Scheme 8: Removal of Boc protection in calixarenes 37–41; (i) CF3CO2H, dichloromethane, rt, then NaHCO3/H2O.
Scheme 9: Synthesis of triazolated tetraureacalix[4]arenes 47–51. Conditions: (i) p-tolyl isocyanate, toluene...
Figure 4: Planar and energy-minimized structures (with CHCl3 molecule included and triazole groups highlighte...
Figure 5: Planar structures of homodimers 482, 512, and heterodimer 48·52 (a); fragment of the 1H NMR spectru...
Figure 6: Planar structures of homodimers 472, 502, and heterodimer 47·52 (a); fragment of the 1H NMR spectru...
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
- coordination chemistry. Shinkai reported that the reactions of 4- and 3-pyridyloxacalix[3]arenes, protected on the lower rims by esters or methyl ethers, with [1,3-(diphenylphosphine)propane]palladium(II) salts gave dimeric capsules linked by three Pd(II) ions at the 4-pyridyl groups (46, Figure 14) or 3
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].
