Synthesis and alkali metal binding properties of "upper rim" functionalized calix[4]arenes

Conner, Mark D.; Janout, Václav; Regen, Steven L.

doi:10.1021/jo00039a048

Cited by 53 publications

(26 citation statements)

References 6 publications

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“…These showed lower extractability for Na + than those at the lower rim, while showing comparable extractability for K + and Cs + . [15] This is a typical rim size effect on the extraction. The extraction of trivalent rare earth (RE) ions with the cone conformational calix [4]arene derivative having a phosphonic acid group at the upper rim 28 was carried out by our group.…”

Section: Research On Metal Cation Extraction With Calixarene Derivativesmentioning

confidence: 96%

Review of the Extraction Behavior of Metal Cations with Calixarene Derivatives

Ohto

2010

SERDJ

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Section: Research On Metal Cation Extraction With Calixarene Derivativesmentioning

confidence: 96%

Review of the Extraction Behavior of Metal Cations with Calixarene Derivatives

Ohto

2010

SERDJ

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“…Hydrolysis of compound 9 with NaOt-Bu in n-butanol and DMSO gave racemic inherently chiral aminocalix [4]arene 10 in 95% yield (Scheme 2) [31]. 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].…”

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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“…A key issue in this work was the effect of lower rim substitution on the ability of the receptors to interact with cytochrome c. Starting from tetrahydroxycalix [4]arene, alkylation of the lower rim phenolic hydroxyl groups with three different alkyl chains gave compounds 6a, b, and c. 17 Formylation of 6a-c by 1,1-dichloromethylmethyl ether in the presence of titanium chloride or using Duff conditions gave tetraaldehydes 7a-c, and subsequent oxidation gave tetraacids 8a-c (Scheme 2). The calix [4]arene tetraacids 8 were activated with oxalyl chloride and coupled with cyclic peptide 5 to form the corresponding protected receptors.…”

Section: Synthesis Of Calix[4]arene Tetracarboxylic Acidsmentioning

confidence: 99%

“…The crude product was added to water and then the water was lyophilized to give the title compound 17 60% NaH (11.8 g, 295 mmol) was washed with hexanes (3 ϫ 150 mL). To a suspension of the NaH in dry DMF (450 mL) was added calix [4]arene 26,27 (14.8 g, 34.7 mmol) and the mixture was heated at 70°C for 10 min.…”

Section: Cyclo-(gly-asp(oh)-gly-asp(oh)-3am5nb) (10)mentioning

confidence: 99%