High-Performance liquid chromatographic separation of enantiomers of unusual amino acids possessing cycloalkane or cycloalkene skeletons on a chiral crown ether containing stationary phase

Török, G.; Péter, Antal; Fülöp, Ferenc

doi:10.1007/bf02467510

Cited by 12 publications

(1 citation statement)

References 28 publications

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“…A simple HPLC method was developed for the separation and identification of the (1 S ,2 R ), (1 R ,2 S ), (1 S ,2 S ), and (1 R ,2 R ) enantiomers of 2-ACPC by using precolumn derivatization with the chiral derivatizing reagents N -(2,4-dinitro-5-fluorophenyl)- l -alaninamide (Marfey's reagent) and 2,3,4,6-tetra- O -acetyl-β- d -glucopyranosyl isothiocyanate . Analogue and homologue derivatives can also be detected by this method. , A newly developed derivatizing agent DANI, (1 S ,2 S )-1,3-diacetoxy-1-(4-nitrophenyl)-2-propylisothiocyanate, likewise proved highly applicable for precolumn derivatization . The two enantiomers of cispentacin can be determined in rat urine by reverse-phase HPLC after derivatization with Marfey's reagent .…”

Section: Transformationsmentioning

confidence: 99%

The Chemistry of 2-Aminocycloalkanecarboxylic Acids

2001

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Section: Transformationsmentioning

confidence: 99%

The Chemistry of 2-Aminocycloalkanecarboxylic Acids

2001

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Evaluation of norbornene- β-cyclodextrin-based monomers and oligomers as chiral selectors by means of nonaqueous capillary electrophoresis

et al. 2001

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Norbornen-5-yl carboxylic acid and norbornen-5-ylmethylsilyl ether-based beta-cyclodextrins (beta-CDs) containing up to three norbornene ester and up to five norbornene silyl ether units have been prepared from beta-CD and norbornen-5-carboxylic chloride and norbornen-5-ylmethyldichlorosilane, respectively. Oligomers (n = 2-4) were prepared therefrom using ring-opening metathesis polymerization (ROMP). Monomeric and oligomeric substituted beta-CDs were evaluated as chiral selectors in nonaqueous capillary zone electrophoresis using 35 mM sodium bicarbonate in N-methylformamide (NMF) as background electrolyte. Both monomeric and oligomeric norbornene ester- and norbornene silyl ether-type selectors showed good enantioresolution for dansylated (DNS-) amino acids using concentrations of the chiral selector of up to 4% w/v. A significant improvement in resolution was observed upon the introduction of up to five norbornene silyl ether units into a beta-CD molecule, whereas higher degrees of substitution with norbornen-5-yl-carboxyl groups lead to a reduction in enantioresolution of DNS-amino acids. Thus, pentakis(norbornen-5-ylmethylhydroxysiloxyl)-beta-CD turned out to be superior to mono(norbornen-5-ylmethylhydroxysiloxyl)-beta-CD in terms of enantioresolution. Moreover, norbornene silyl ether-type selectors were found to be more efficient than norbornene ester-type selectors. Finally, oligomeric selectors were found to possess superior or at least comparable enantioselectivity in the separation of DNS-amino acids compared to the parent monomers. A maximum in enantioresolution was obtained with oligo(pentakis(norbornen-5-ylmethylhydroxysiloxyl)beta-CD).

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Synthesis of Carbocyclic β‐Amino Acids

Kiss

Forró

Fülöp

2009

Amino Acids, Peptides and Proteins in Organic Chemistry

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j367 acids was reviewed by our group in 2001 [1]; the present chapter highlights the chemistry of these compounds published since 2000, with the aim of offering the reader an insight into the most recent developments in this field. Synthesis of Carbocyclic b-Amino AcidsOwing to their significance, a number of methods have been developed for the synthesis of these conformationally restricted molecules in racemic and enantiomerically pure form. The largest groups of carbocyclic b-amino acids and the most intensively investigated are the fiveand six-membered derivatives. One main method of preparation consists of the amidation of 1,2-dicarboxylic anhydrides 4, followed by Hoffmann rearrangement of the resulting amide 5 to amino acid 7. The same starting material, the meso anhydride 4, undergoes partial hydrolysis, followed by the Curtius rearrangement, to give 2-aminocyclohexanecarboxylic acid 7 (Scheme 8.1) ([1] and references cited therein).A widely used method for the synthesis of carbocyclic b-amino acids is the transformation of cycloalkenes via the corresponding bicyclic b-lactams. The 1,2dipolar cycloaddition of chlorosulfonyl isocyanate (CSI) to cycloalkenes 8 led regioselectively to the cycloalkane-fused b-lactams 10, whose acidic hydrolysis resulted in lactam ring opening and formation of the carbocyclic b-amino acid hydrochlorides 11 (Scheme 8.2) ([1] and references cited therein). O O O NH 4 OH COOH CONH 2 1. ROH 2. HO 3. H COOR COOH Curtius degradation COOH NH 2 Hoffmann degradation NaOH, Br 2 1. SOCl 2 2. NaN 3 Dowex 4 5 6 7 Scheme 8.1 Synthesis of carbocyclic b-amino acids by Curtius and Hoffmann rearrangements. CSI NSO 2 Cl O H 2 O NH O HCl, RT COOH NH 2 HCl 8 9 10 11 Scheme 8.2 Synthesis of carbocyclic b-amino acids from b-lactams. 368j 8 Synthesis of Carbocyclic b-Amino Acids 15 16 18 17 16:17:18 = 95.5:1.7:2.8 KOtBu, tBuOH ∆, 3hScheme 8.4 Synthesis of 3-methylcispentacin derivatives by conjugate addition. Synthesis of Carbocyclic b-Amino Acids j369To prepare 3-methyltranspentacin, aminocarboxylate 17 was first obtained in a larger quantity from diastereoisomer 16 by epimerization on treatment with KOtBu in tBuOH; this afforded 17 in quantitative yield and a diastereomeric excess of 99%. N-Deprotection of 17, followed by ester hydrolysis, gave the desired 3-methyltranspentacin in 97% e.e. [9].By using this conjugate addition methodology, Davies et al. also prepared 5-substituted derivatives of cispentacin. The addition of lithium amide (S)-13 to 5-isopropyl-, 5-phenyl-, and 5-tert-butylcyclopentenecarboxylates proceeded with a high degree of selectivity, the major derivatives formed having the amine anti to the 5-alkyl group. N-Deprotection by hydrogenolysis, subsequent acid hydrolysis of the ester, and ion-exchange chromatography furnished 5-substituted cispentacin derivatives in 98% e.e. [10].The asymmetric synthesis of a series of functionalized derivatives was achieved by using amine conjugate addition processes. Four stereoisomers of 2-amino-5carboxymethylcyclopentanecarboxylate were prepared ...

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High-Performance liquid chromatographic separation of enantiomers of unusual amino acids possessing cycloalkane or cycloalkene skeletons on a chiral crown ether containing stationary phase

Cited by 12 publications

References 28 publications

The Chemistry of 2-Aminocycloalkanecarboxylic Acids

The Chemistry of 2-Aminocycloalkanecarboxylic Acids

Evaluation of norbornene- β-cyclodextrin-based monomers and oligomers as chiral selectors by means of nonaqueous capillary electrophoresis

Synthesis of Carbocyclic β‐Amino Acids

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