Synthesis of Calix[4]arenylvinylene and Calix[4]arenylphenylene Oligomers by Stille and Suzuki Cross-Coupling Reactions

Dondoni, Alessandro; Ghiglione, Chiara; Marra, Alberto; Scoponi, Marco

doi:10.1021/jo980868w

Cited by 39 publications

(60 citation statements)

References 38 publications

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“…1,6‐Bis[25,26,27‐tripropoxy‐28‐(oxy)calix[4]arene]hexane (2) : Solid 1,6‐bis[( p ‐tolylsulfonyl)oxy]hexane16 (127 mg, 0.25 mmol) was added to a stirred mixture of 25,26,27‐tripropoxy‐28‐hydroxy‐calix[4]arene15 ( 1 ) (275 mg, 0.5 mmol) and NaH (24 mg, 1.0 mmol) in anhydrous THF (10 mL). The mixture was refluxed for 24 h. The progress of the reaction was monitored by following the disappearance of the calixarene reagent by TLC (cyclohexane/CH 2 Cl 2 , 7:3, v/v).…”

Section: Methodsmentioning

confidence: 99%

Sequence, Stoichiometry, and Dimensionality Control in Porphyrin/Bis‐calix[4]arene Self‐Assemblies in Aqueous Solution

D’Urso¹,

Cristaldi²,

Fragalà³

et al. 2010

Chemistry A European J

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The use of a water-soluble octacationic bis-calix[4]arene with divergent cavities (BC(4)) as a templating agent for the assembly of a tetraanionic porphyrin (CuTPPS) has allowed the noncovalent synthesis of 2D or 3D multiporphyrin assemblies. Self-assembly of CuTPPS and BC(4) molecules proceeded under hierarchical control in a stepwise fashion to yield discrete and isolable supramolecular nanostructures containing up to 33 molecular elements (i.e., the CuTPPS/BC(4) 17:16 assembly, obtained in less than three hours). The formation of these species could be conveniently monitored by means of UV/Vis spectroscopy by following the absorbance of the Soret band at 412 nm. In particular, the attainment of the pivotal CuTPPS/BC(4) 5:4 species with a cruciform structure, as the key fork-point intermediate for the subsequent formation of the higher 2D and 3D assemblies, has been demonstrated by light-scattering studies and by an unequivocal synthesis of mixed-porphyrin/calixarene 5:4 species involving the use of two different types of metallated porphyrins, namely CuTPPS and MnTPPS. The remarkable stability of these assemblies permits a stepwise synthesis that makes it possible to choose the desired porphyrin sequence.

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Section: Methodsmentioning

confidence: 99%

Sequence, Stoichiometry, and Dimensionality Control in Porphyrin/Bis‐calix[4]arene Self‐Assemblies in Aqueous Solution

D’Urso¹,

Cristaldi²,

Fragalà³

et al. 2010

Chemistry A European J

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“…Starting from compound 7, the meta-cyano substituted inherently chiral aminocalix [4]arene derivative 11 could be easily obtained in 62% yield by the Pd-catalyzed nucleophilic substitution reaction with CuCN [32]. Whereas the preparation of the meta-phenyl substituted inherently chiral aminocalix [4]arene 13 was achieved in 67% yield via Suzuki coupling reaction of 7 and phenylboric acid in the presence of Pd(PPh 3 ) 4 and sodium carbonate [33]. Under the same hydrolysis conditions, compound 11 or 13 could be converted into racemic 12 in 78% yield or racemic 14 in 92% yield, respectively (Scheme 3).…”

Section: Synthesis Of Racemic Meta-substituted Inherently Chiral Aminmentioning

confidence: 99%

“…Bromination of 17 with an excess of NBS in 2-butanone at room temperature gave the diastereomer 18 as a mixture in 83% total yield. Diasteromer 18 reacted with CuCN [32] and PhB(OH) 2 [33] under the Pd-catalyzed conditions to give the diastereomers 19 (19a+19b) and 20 (20a+20b), respectively, which could all be readily separated by common chromatography. Enantiopure antipodes 12a/12b and 14a/14b were then obtained by the hydrolysis of 19a/19b and 20a/20b with NaOt-Bu in n-BuOH and DMSO, respectively.…”

Section: Resolution Of Meta-cyano and Phenyl Substituted Inherently Cmentioning

confidence: 99%

Efficient synthesis and resolution of meta-substituted inherently chiral aminocalix[4]arene derivatives

Zhang

Huang

et al. 2010

Chin. Sci. Bull.

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Efficient synthesis and resolution of a series of meta-substituted inherently chiral aminocalix[4]arene derivatives have been described. Consequently, the meta-nitro, bromo and chloro substituted inherently chiral calix [4]arenes could be directly synthesized by the nitration, bromination, and chlorination of the acylating product of aminocalix[4]arene. meta-Cyano and phenyl substituted inherently chiral aminocalix[4]arenes were readily obtained by the nucleophilic substitution reaction or Suzuki coupling reaction from the meta-bromo substituted one under the Pd-catalyzed conditions. For kinetic resolution of the racemic inherently chiral aminocalix[4]arenes, it was found that the electron-withdrawing ability of substituent was helpful to improving the resolution efficiency of the acylation process, and the kinetic resolution could be efficiently applied to the resolution of meta-nitro substituted inherently chiral aminocalix[4]arene, providing (cS)-or (cR)-isomer in up to 95% or 99.9% ee value, respectively, with the corresponding chiral acylating reagent. Moreover, by introduction of the chiral auxiliary, enantiopure antipodes of meta-cyano and phenyl substituted inherently chiral aminocalix[4]arenes could also be readily obtained. These enantiopure aminocalix[4]arenes are potential building blocks for constructing novel chiral receptors and asymmetric catalysts. inherently chiral calixarenes, kinetic resolution, synthesis Citation: Xu Z X, Zhang C, Huang Z T, et al. Efficient synthesis and resolution of meta-substituted inherently chiral aminocalix[4]arene derivatives.Calixarenes are a versatile class of macrocyclic compounds that have been studied extensively, both as host materials and as building blocks for the synthesis of designed specific receptors [1,2]. The introduction of chirality in calixarenes should create platforms for the potential enantioselective recognition of chiral guests and asymmetric catalysis [3][4][5][6][7]. Besides the functionalization with chiral moieties [8], inherently chirality originates from the asymmetric array of achiral residues on the calixarene skeletons, which have attracted much attention for their unique structure and potential applications in chiral recognition and asymmetric catalysis.Since Gutsche and co-workers [9] reported the first example of inherently chiral calix[4]arene in 1982, there have been several different approaches to inherently chiral calyx-*Corresponding author (email: cchen@iccas.ac.cn) arenes in the literature [10][11][12]. However, their optical resolution was usually achieved by using the HPLC methods [1,13], which was inappropriate for scale-up and thus impeded their practical applications. In recent years, we [14][15][16][17][18] and other groups [19][20][21][22][23][24][25] reported a convenient approach to enantiopure inherently chiral calixarene derivatives by introduction of a chiral auxiliary and then separation of subsequent diasteromers via column chromatography on silica gel, preparative TLC, or even simple crystallization. This approac...

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“…(10) 19.850 (7) 10.620(6) b (Å ) 25.276 (10) 26.185 (7) 17.585(6) c (Å ) 11.501 (10) A mixture of 5 mL of a 2:5 £ 10 24 M aqueous picrate solution and 5 mL of a 2:5 £ 10 24 M solution of calixarene in CH 2 Cl 2 was vigorously agitated in a stoppered glass tube with a mechanical shaker for 2 min, then magnetically stirred in a thermostated water bath at 20^0:18C for 30 min, and finally left standing for an additional 30 min. The concentration of picrate ion remaining in the aqueous phase was then determined spectrophotometrically described as previously (maximum absorption of the picrate ion at 355 nm, 1 ¼ 14 285 mol 21 L cm 21 ).…”

Section: Picrate Extraction Measurementsmentioning

confidence: 99%

First Synthesis of 1,3-Alternate 25,27-Dialkyloxy-5,17-diarylcalix[4]arenes-crown-6 as New Cesium Selective Extractants by Suzuki Cross-coupling Reaction

Guillon

Léger

Dapremont

et al. 2004

Supramolecular Chemistry

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The synthesis of new 25,27-dialkyloxy-5,17-diarylcalix[4]arenes-crown-6 1a -f in 1,3-alternate conformation by Suzuki cross-coupling reaction is reported. Their conformation was determined using 1 H, 13 C, 2D NMR and ROESY analysis, and X-ray crystallography. Extraction experiments using a two-phase solvent method involving sodium, potassium or cesium picrate showed good extraction of the cesium cation. The X-ray crystal structures of 1,3-alternate 25,27-dipropoxy-5,17-diphenylcalix[4]arene-crown-6 ether 1a and its cesium picrate complex were established. Solid-state data were used to determine the complexation behavior of these new ligands. The efficiency of calixarenes 1a -f for cesium ion extraction could be ascribed to the rigidity and flatness linkages caused by the aryl groups at the lower rim of the aromatic moieties in the calixarene skeleton. In addition, the introduction of these aromatic moieties in positions 5 and 17 enhanced the solubility of the metal complexes in organic media.

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Synthesis of Calix[4]arenylvinylene and Calix[4]arenylphenylene Oligomers by Stille and Suzuki Cross-Coupling Reactions

Cited by 39 publications

References 38 publications

Sequence, Stoichiometry, and Dimensionality Control in Porphyrin/Bis‐calix[4]arene Self‐Assemblies in Aqueous Solution

Sequence, Stoichiometry, and Dimensionality Control in Porphyrin/Bis‐calix[4]arene Self‐Assemblies in Aqueous Solution

Efficient synthesis and resolution of meta-substituted inherently chiral aminocalix[4]arene derivatives

First Synthesis of 1,3-Alternate 25,27-Dialkyloxy-5,17-diarylcalix[4]arenes-crown-6 as New Cesium Selective Extractants by Suzuki Cross-coupling Reaction

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