• Bulletin of the Korean Chemical Society
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• v.27 no.10
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• pp.1577-1580
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• 2006

The article reports the synthesis and enantiomeric recognition of a new chiral azophenolic pyridino-18-crown-6 ether, (S,S)-6, possessing diphenyl groups as chiral barriers. The association constants for the enantiomeric recognition of chiral primary amines (7-12) using chiral azophenolic pyridino-18-crown-6 ether, (S,S)-6, were determined by UV-visible titration method in acetonitrile at $25{^{\circ}C}$.

• Bulletin of the Korean Chemical Society
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• v.16 no.4
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• pp.305-309
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• 1995

The enantiomeric separation of several amino acid derivatives by reversed-phase liquid chromatography using two (R)-and (S)-naphthylethylcarbamate-β-cyclodextrin(NEC-β-CD) bonded stationary phases was studied to illustrate the chiral recognition model of the enantiomeric separation. The retention and enantioselectivity of the chiral separations with (R)-and (S)-NEC-β-CD bonded phases were compared with similar separations with the native β-CD stationary phases. Especially, the enantioselectivity and elution orders between the derivatized amino acid enantiomers are carefully examined. These results can be illustrated by the chiral recognition models involving inclusion complexation, π-π interaction, and/or hydrophobic interaction. Inclusion complexation and hydrophobic interaction of the naphthyl group of the NEC moiety seem to be major chiral recognition components in the enantiomeric separation of 2,4-dinitrophenyl amino acids and dabsyl amino acids on (R)-and (S)-NEC-β-CD columns. For dansyl amino acids, only the inclusion complexation is the dominant factor. Three different chiral recognition models containing π-π interaction, inclusion complexation and hydrogen bonding were proposed for the separation of the 3,5-dinitrobenzoyl amino acid enantiomers, depending on the size and shape of amino acids.

• Bulletin of the Korean Chemical Society
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• v.29 no.5
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• pp.1069-1072
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• 2008

• Bulletin of the Korean Chemical Society
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• v.24 no.1
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• pp.95-98
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• 2003

Enantioselectivity of the propranolol on β-cyclodextrin was simulated by molecular modeling. Monte Carlo (MC) docking and molecular dynamics (MD) simulations were applied to investigate the molecular mechanism of enantioselective difference of both enantiomeric complexes. An energetic analysis of MC docking simulations coupled to the MD simulations successfully explains the experimental elution order of propranolol enantiomers. Molecular dynamics simulations indicate that average energy difference between the enantiomeric complexes, frequently used as a measure of chiral recognition, depends on the length of the simulation time. We found that, only in case of much longer MD simulations, noticeable chiral separation was observed.

• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1551-1554
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• 2010

Two diastereomeric chiral stationary phases (CSPs) were applied to the liquid chromatographic resolution of various racemic ${\alpha}$-amino methyl esters, ${\alpha}$-amino N,N-diethylamides and ${\alpha}$-amino N-propylamides. The CSP incorporating (R)-3,3'-diphenyl-1,1'-binaphtyl and (R,R)-tartaric acid unit as chiral barriers did not show any chiral recognition. In contrast, the CSP incorporating (R)-3,3'-diphenyl-1,1'-binaphtyl and (S,S)-tartaric acid unit as chiral barriers was found to show excellent chiral recognition especially for the two enantiomers of ${\alpha}$-amino N-propylamides. Some of ${\alpha}$-amino methyl esters and ${\alpha}$-amino N,N-diethylamides were also resolved on the CSP incorporating (R)-3,3'-diphenyl-1,1'-binaphtyl and (S,S)-tartaric acid unit. From these results it was concluded that the two chiral units composing the diastereomeric CSPs can show "matched" or "mismatched" effect on the chiral recognition according to their absolute stereochemistry.

• Journal of the Korean Society of Industry Convergence
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• v.12 no.3
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• pp.143-147
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• 2009

The enantioselective reduction of representative prochiral alkyl-aryl ketones with a new chiral alkoxy-amine-aluminum derivatives from aluminum hydride and ${\alpha},{\alpha}$-diphenyl-${\beta}$-amino alcohols, such as (S)-(-)-2-amino-3-methyl-1,1-diphenylbutan-1-ol(AMDPB) and (S)-(-)-2-(diphenylhydroxy-methyl)pyrrolidine(DPHMP), in THF at $0^{\circ}C$ was studied. In the reduction of alkoxy-amine-aluminum derivatives, acetophenone, propiophenone, isopropiophenone, and butyrophenone are reduced to corresponding aromatic secoundary alcohols with 34~60 % enantiomeric excess of (S)-isomers. For such ketones, the optical induction was enhanced by increasing a size of alkyl groups.

• Bulletin of the Korean Chemical Society
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• v.17 no.11
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• pp.1052-1056
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• 1996

The effects of β-CD, Me-β-CD, and biphenyl capped β-CD on 1H NMR spectra of mandelic acid 1, α-methylbenzylamine 2 and 2-phenylpropionic acid 3 were investigated. Enantiomeric recognition was observed for mandelic acid 1 by all the hosts used, for α-methylbenzylamine 2 by β-CD and Me-β-CD, and for 2-phenylpropionic acid 3 by Me-β-CD. In the presence of biphenyl-capped β-CD, ο-, m-, and p-protons of the phenyl groups of the guests are discriminated due to ring current of the capped biphenyl group. The splitting pattern of the phenyl protons indicates that the phenyl group of the guests is inserted into the β-CD cavity from the secondary hydroxyl side and positioned in close proximity to the capped biphenyl ring. The magnitude of the upfield shifts of H3 and H5 protons of β-CD upon binding of guests 1-3 is similar to that caused by ephedrine or pseudoephedrine, suggesting that the substitution at benzylic carbon atom has little effect on the depth of the insertion of the phenyl group into the β-CD cavity and stability of the inclusion complexes.

• Bulletin of the Korean Chemical Society
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• v.13 no.4
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• pp.407-413
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• 1992

The chromatographic separation of the stereoisomers of the N-(3,5-dinitrobenzoyl) derivatives of fifteen dipeptide methyl esters and nine dipeptide alkyl esters was investigated on three different chiral stationary phases derived from N-acylated ${\alpha}-arylalkylamines$. Two of these CSPs contain second stereogenic centers. These secondary stereogenic centers of CSPs were proposed to provide secondary effects in terms of chiral recognition. From the elution orders of the four dipeptide stereoisomers and the separation factors of the enantiomeric pairs of the N-(3,5-dinitrobenzoyl) derivatives of the dipeptide alkyl esters having different alkoxy substituents, it was proposed that the intercalation of the alkoxy substituents of dipeptide derivatives between the connecting arm of CSPs may control the magnitude of chiral separations of dipeptide derivatives.

• Journal of the Korean Chemical Society
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• v.39 no.2
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• pp.94-102
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• 1995

S-Hydroxypropyl(PH) ${\beta}$-cyclodextrin(hydrophilic), dialkyl(DA)-cyclodextrin(hydrophobic), trifluoroacetyl(TA) ${\gamma}$-cyclodextrin(intermediate) stationary phases were used for gas chromatographic separation of racemic alcohols and their derivatives. All the alcohols used for this experiment were derivatived by using trifluoro acetic anhydride, acetic anhydride, or trichloro acetic anhydride. It is apparent that the enantioselectivity of the enantiomeric pairs was very dependent on the type of acylation reagent. The best experimental condition of optical resolution of the alcohols and their derivatives was different on the polarity of the solute molecules. The chiral separation was also studied depending on temperature, polarity of the column, and hydrogen bonding ability and steric effect between the alchols and CD stationary phase. The chiral recognition mechanism is dependent not upon the kinds of the chiral stationay phases but upon the derivatization of the racemic alchols.

• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.3017-3021
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• 2011

Two chiral stationary phases (CSPs) based on (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6 bonded covalently to silica gel were applied for the first time to the resolution of racemic vigabatrin and its analogue ${\gamma}$-amino acids and the resolution results were compared to those on the commercially available Crownpak CR(+) based on (3,3'-diphenyl-1,1'-binaphthyl)-20-crown-6 coated dynamically onto octadecylsilica gel. While vigabatrin was not resolved at all on Crownpak CR(+), it was resolved quite well on the two CSPs. Among four vigabatrin analogue ${\gamma}$-amino acids, only two were resolved on Crownpak CR(+), but three were resolved on the CSP (CSP 1) containing residual silanol groups and all of four were resolved on the CSP (CSP 2) containing residual silanol group-protecting n-octyl groups. The improved lipophilicity in CSP 2 was proposed to be responsible for its superiority to CSP 1 for the resolution of vigabatrin and analogue ${\gamma}$-amino acids. In addition, the composition of aqueous mobile phase was found to affect the chiral recognition behaviors for the resolution of vigabatrin and analogue ${\gamma}$-amino acids on CSP 2.