Facile, high-yielding synthesis of deepened cavitands: a synthetic and theoretical study

Csók, Zsolt; Kégl, Tamás; Pa̋rkányi, László; Varga, Ágnes; Kunsági‐Máté, Sándor; Kollár, László

doi:10.1080/10610278.2011.593633

Cited by 15 publications

(4 citation statements)

References 39 publications

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“…The synthesis of this compound is a four-step consecutive reaction sequence ( Figure 1 ) started from small organic molecules. The first step is an acid-catalyzed condensation reaction of 2-methylresorcinol and acetaldehyde [ 36 ], the second step is alkylating the hydroxyl groups with bromochloromethane [ 37 ], the third step is a radical bromination of the methyl groups on the upper rim [ 38 ] with N -bromosuccinimide and the last step is a Williamson etherification with 4-iodophenol [ 39 ]. Each step can be performed with excellent (70–80%) yield.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Novel Cavitand Host Molecules via Palladium-Catalyzed Aryloxy- and Azidocarbonylation

2022

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Novel, elongated, resorcine[4]arene-based cavitands were synthesized via various consecutive reaction steps, including homogeneous catalytic aryloxy- and azidocarbonylation processes. The effects of carbon monoxide pressure and temperature on the conversion were examined in aryloxycarbonylation. It was revealed that a reaction temperature of 100 °C is required to achieve complete conversion both with monodentate (PPh3) and bidentate (Xantphos) phosphines at different carbon monoxide pressures (1–40 bar). Using ten different phenols as O-nucleophiles, partial hydrolysis of the esters to the corresponding carboxylic acids took place—i.e., 58–90% chemoselectivities toward esters were obtained. Moreover, the influences of temperature, reaction time and the catalyst ratio on the selectivity and conversion were described in the case of azidocarbonylation reaction. The formation of the acyl azide with high chemoselevtivity can be achieved at room temperature only. The higher reaction temperatures (50 °C) and higher catalyst loadings favor the formation of the primary amide. The characterization of the target compounds (esters and acyl azides) was carried out by IR and 1H and 13C NMR. The discussion of the influences of various parameters is based on in situ NMR investigations.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Novel Cavitand Host Molecules via Palladium-Catalyzed Aryloxy- and Azidocarbonylation

2022

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“…In a previous study of our research group a similar but smaller cavitand structure was examined with X‐ray crystallography and theoretical PBEPBE/6‐31G(d,p) methods where the cavitand contained a simple aromatic wall builded up by phenyl groups. In this study it had been proved in both experimental and theoretical ways that intramolecular T‐shaped π ‐stacking interactions were established between the phenyl groups and the geometry showed C 4 symmetry structure.…”

Section: Resultsmentioning

confidence: 99%

The Role of Weak Interactions in Supramolecular Compounds: A Synthetic and Theoretical Study of Novel Elongated Cavitands

et al. 2017

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A new resorcinol-based tetraazidocavitand (2) has been prepared via substitution reaction started from the corresponding tetrabromocavitand (1). This tetraazidocavitand was used as a starting material for azide-alkyne cycloaddition with different alkynes and this way four novel deepened cavitands have been synthesized under mild conditions. Molecular dynamics, semiempirical PM6 and DFT PBEPBE/6-31G(d,p) studies have been carried out for these new triazole ring containing structures to reveal the exact geometry in solution, furthermore theoretical NMR chemical shift calculations were completed at B3LYPÀD3/6-31G(d,p) GIAO level in order to compare with the experimental NMR data. QTAIM analysis at B3LYPÀD3/def2-TZVP level was performed and NCI isosurfaces were generated to reveal the potential intramolecular weak interactions between the cavitand branches.

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“…TAC was synthesized as previously described [ 20 ]. The synthesis of TDC is based on the Williamson-type ether synthesis, reacting tetrabromo-cavitand [ 21 , 22 ] with dimethyl 5-hydroxyisophthalate, followed by the hydrolysis of the ester functionalities. Fluorimetric measurements were applied to determine the thermodynamic parameters of the PHX–cavitand complex formation reaction.…”

Section: Introductionmentioning

confidence: 99%

Weak Interactions of the Isomers of Phototrexate and Two Cavitand Derivatives

Preisz

Nagymihály

Kollár

et al. 2021

IJMS

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The interactions of two conformers of newly synthesized photoswitchable azobenzene analogue of methotrexate, called Phototrexate, with two cavitand derivatives, have been investigated in dimethyl sulfoxide medium. Photoluminescence methods have been applied to determine the complex stabilities and the related enthalpy and entropy changes associated to the complex formation around room temperature. Results show opposite temperature dependence of complex stabilities. The structure of the upper rims of the host molecules and the reordered solvent structure were identified as the background of the opposite tendencies of temperature dependence at molecular level. These results can support the therapeutic application of the photoswitchable phototrexate, because the formation of inclusion complexes is a promising method to regulate the pharmacokinetics of drug molecules.

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Facile, high-yielding synthesis of deepened cavitands: a synthetic and theoretical study

Cited by 15 publications

References 39 publications

Synthesis of Novel Cavitand Host Molecules via Palladium-Catalyzed Aryloxy- and Azidocarbonylation

Synthesis of Novel Cavitand Host Molecules via Palladium-Catalyzed Aryloxy- and Azidocarbonylation

The Role of Weak Interactions in Supramolecular Compounds: A Synthetic and Theoretical Study of Novel Elongated Cavitands

Weak Interactions of the Isomers of Phototrexate and Two Cavitand Derivatives

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