Synthesis of New Chiral Ligands by Capping of Calix[4]arene Derivatives

Pinkhassik, Evgueni; Stibor, Ivan; Havlı́ček, Vladimı́r

doi:10.1135/cccc19961182

Cited by 9 publications

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“…Initially we attempted the synthesis of upper rim binaphthyl bridged calix[4]arenes, by the reaction of the diaminocalix[4]arene 1 with dichloride ( R , S )- 3 , using a number of classical experimental procedures for the acylation of amines, but without any success (Scheme ). However, the reaction of the diamine 1 with several monofunctional acylating agents except 2 , runs smoothly …”

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confidence: 99%

Synthesis of Upper and Lower Rim Binaphthyl Bridged Calix[4]arenes: New Potential Chiral Hosts for Molecular Recognition and Catalysis

Pinkhassik¹,

Stibor²,

Casnati³

et al. 1997

J. Org. Chem.

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New chiral upper and lower rim (R)-binaphthyl-bridged calix[4]arenes in the cone conformation (5, 10, 11, 15, 17, 18) have been synthesized by exploiting the selective functionalization of the calix[4]arene skeleton. The conformational properties of the new hosts in CDCl3 and DMSO-d 6 have been clarified by dynamic NMR measurements, and their complexation properties toward neutral molecules, alkali metal, and silver(I) cations have been explored. The upper rim binaphthyl-bridged calix[4]arene 5 is able to form a 1:1 complex with Ag+ in CDCl3:CD3OD 1:1 v/v solution, where the silver cation is encapsulated into the apolar cavity. The determined association constant (log K = 3.51) is substantially higher than for unbridged calix[4]arenes in the cone conformation. These new macrobicyclic compounds are potential hosts for chiral recognition and catalysis.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Upper and Lower Rim Binaphthyl Bridged Calix[4]arenes: New Potential Chiral Hosts for Molecular Recognition and Catalysis

Pinkhassik¹,

Stibor²,

Casnati³

et al. 1997

J. Org. Chem.

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“…There has been only one reported example that we are aware of in which amino acids are directly attached to an aminocalixarene through the carboxy termini. 9 However, the compound reported contains alanines on only two of the four aromatic rings of the calixarene and has ethoxy groups at the lower rim, which does not maintain the cone conformation. Our results demonstrate that coupling to all four upper rim positions of the cone aminocalix [4]arene without the use of a spacer is not only possible but efficient.…”

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Solid-Phase Synthesis of a Novel Peptide Substituted Calix[4]arene

Shuker¹,

Esterbrook²,

González³

2001

Synlett

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The described approach provides calix [4]arene scaffolds that can be coupled to amino acids using standard solid phase peptide synthesis, providing a route for the rapid preparation of combinatorial libraries of this class of molecular hosts. In addition, we report the first example of a tetrapeptido-calix[4]arene in which the amino acids are attached to the upper rim through the carboxy termini. Specifically, a tetra-nitrocalix[4]arene was prepared, attached to solid support, and the nitro groups were reduced to the corresponding amines by treatment with SnCl 2 ·H 2 O. This was followed by three successive couplings with alanine to provide the tetra(trialanine)calix[4]arene. The final product was cleaved from the solid support and shown by LCMS to elute as one peak with the expected mass.

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“…Peptide-substituted calixarenes, in particular, are attractive as hosts for molecular recognition because amino acids encompass a diversity of functionality, techniques for the synthesis of peptides have been extensively developed, and their chirality can influence the stereoselectivity of binding. A number of calixarenes substituted with amino acids at the upper rim have been reported. , However, with only one exception that we are aware of, these approaches utilize carboxyl functionality at the upper rim and require coupling to the amino terminus of an amino acid or peptide. Our approach involves the coupling of the carboxyl termini of amino acids to an aminocalixarene, which can be accomplished through standard Fmoc peptide synthesis, as we recently reported for the solid-phase synthesis of a calix[4]arene substituted with tripeptides at the upper rim .…”

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Molecular Recognition in Methanol: The First Example of Hydrogen-Bond-Mediated Self-Association of a Calix[4]arene in Polar, Protic Solvent

Brewster

Shuker

2002

J. Am. Chem. Soc.

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Tetraalaninecalixarene was prepared by coupling of tetraaminocalix[4]arene with alanine. It dimerizes in methanol, providing the first example of a substituted calixarene that undergoes self-association through hydrogen bonding in polar, protic solvent. The association constant in 24:1 MeOH:H2O was determined to be 29 000 M-1. Addition of arginine or lysine results in disruption of the dimer and formation of a 1:1 complex between the amino acid and the tetraalaninecalixarene. The preparation of a peptidocalixarene that associates in polar solvent opens new doors for the use of calixarenes for molecular recognition in biologically relevant environments.

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Synthesis of New Chiral Ligands by Capping of Calix[4]arene Derivatives

Abstract: Calix[4]arene derivatives are used as a scaffold for the attachment of chiral substituents. Calix[4]arenes having either lower or upper rim capped with chiral binaphtholic species 5 and 6, as well as new biscalix[4]arenodiaza-18-crown-6 (8), have been synthesized.

Cited by 9 publications

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Synthesis of Upper and Lower Rim Binaphthyl Bridged Calix[4]arenes: New Potential Chiral Hosts for Molecular Recognition and Catalysis

Synthesis of Upper and Lower Rim Binaphthyl Bridged Calix[4]arenes: New Potential Chiral Hosts for Molecular Recognition and Catalysis

Solid-Phase Synthesis of a Novel Peptide Substituted Calix[4]arene

Molecular Recognition in Methanol: The First Example of Hydrogen-Bond-Mediated Self-Association of a Calix[4]arene in Polar, Protic Solvent

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