Computational studies on chiral discrimination mechanism of cellulose trisphenylcarbamate

Yashima, Eiji; Yamada, Makiko; Kaida, Yuriko; Okamoto, Yoshio

doi:10.1016/0021-9673(94)01039-h

Cited by 90 publications

(75 citation statements)

References 28 publications

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“…[87,88] The calculations suggested that the lowest or averaged interaction energy between CTPC and (S,S)-69 is lower than that between CTPC and (R,R)-69, whereas a reversed enantiomer preference was observed for CDMPC and 69. This indicates that (S,S)-69 may interact more closely with CTPC than (R,R)-69, which in turn interacts more strongly with CDMPC.…”

Section: Computational Studiesmentioning

confidence: 99%

“…We recently carried out MM calculations on the interaction energies between CTPC [87] or CDMPC [88] and trans-stilbene oxide (69) or trans-1,2-diphenylcyclopropane (93) to gain insight into the mechanism for the recognition of chirality on CDCl 3 -insoluble phenylcarbamate derivatives. CTPC is a good candidate for such a study, because its structure was postulated on the basis of an X-ray analysis [45] and it shows a high ability to recognize chirality for HPLC as a CSP as well as a CDMPC.…”

Section: Computational Studiesmentioning

confidence: 99%

See 1 more Smart Citation

Polysaccharide Derivatives for Chromatographic Separation of Enantiomers

Okamoto

Yashima

1998

Angewandte Chemie International Edition

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910

355

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The first resolution of enantiomers was performed 150 years ago-mechanically. Today a powerful method for carrying out this task is HPLC on polysaccharide derivatives as chiral stationary phases. Most racemates, from an analytical to a preparative scale, now appear to be resolved by this technique. As an example, the chromatogram for the enantiomeric resolution of a fullerene derivative is shown on the right.

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Section: Computational Studiesmentioning

confidence: 99%

Section: Computational Studiesmentioning

confidence: 99%

Polysaccharide Derivatives for Chromatographic Separation of Enantiomers

Okamoto

Yashima

1998

Angewandte Chemie International Edition

Self Cite

910

355

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“…Computational studies have also been conducted on chiral discrimination of cellulose trisphenylcarbamate CSPs where the authors calculated interaction energies and correlated it with chromatographic resolution. 11 Thus studies have been attempted using X-ray crystal structure analysis and molecular modeling 12 and used to generate empirical threedimensional structures of solution state complexes. 9,13 Although these molecular mechanics approach have produced some interesting results, it is inherently very complicated in nature and cannot be applied for the simple and routine study of the complex formation phenomenon.…”

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confidence: 99%

Comparison of cyclodextrin-barbiturate noncovalent complexes using electrospray ionization mass spectrometry and capillary electrophoresis

Srinivasan

Bartlett

2000

Rapid Commun. Mass Spectrom.

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Various noncovalent complexes between native and derivatized cyclodextrins (CDs) and barbiturates were studied using capillary electrophoresis (CE) and electrospray ionization mass spectrometry (ESI-MS). This paper involves the study of four aspects of CD-barbiturate noncovalent inclusion complexes. The first study focused on determining the formation of CD-barbiturate inclusion complexes in ESI-MS. This determination was accomplished by the comparison of migration data from CE with ESI-MS inclusion complex peak abundances, which were found to be complementary. The second study found the possibility of predicting native beta-CD mediated CE elution orders for barbiturates using data from ESI-MS. A third study focused on the formation of barbiturate inclusion complexes with derivatized beta-CD and gamma-CD. As part of this study, the effect of the extent of side chain substitution on native CD complexation behavior was investigated. The results indicated that the number of side chains on the CD does not affect the formation of barbiturate complexes with the hydrophobic CD cavity. Finally, a comparison of the hydroxypropyl-beta-CD-barbiturate and hydroxypropyl-gamma-CD-barbiturate complexes in CE and ESI-MS was made to study the relationship between strength of drug-CD binding and enantioresolution. The results from the above studies indicated that the gas phase and the solution state complexes showed comparable behavior indicating that similar interactions played a role in stabilizing these complexes. While it was possible to use the ESI-MS data to determine drug binding to the CDs, it was not possible to predict whether a separation of the enantiomers of a chiral barbiturate would occur. However, the ESI-MS data could be used to eliminate certain CDs from consideration as chiral selectors.

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“…[5][6][7][8][9] Given the very small energetic difference in the recognition of enantiomers of 1 on the CSP and the inability of calculations of molecular mechanics to simulate mixtures of solvents, computational analysis is not suitable for providing a quantitative model for a large set of analytes. Therefore, the study was aimed to propose models of interaction between the enantiomers of 1 and the Chiralcel OD to explain the recognition mechanism.…”

Section: Molecular Modelingmentioning

confidence: 99%

“…[6][7][8] In this work a model of Chiralcel OD stationary phase was constructed according to a procedure described in another report. 9 Subsequent docking experiments between the CSP model and the enantiomers of compound 1 were carried out in order to elucidate the chiral discrimination mechanism at a molecular level. We propose a chiral recognition mechanism having performed molecular mechanical calculations on the interaction energies between the Chiralcel OD model and the investigated enantiomers.…”

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confidence: 99%

Enantioselective chromatography and absolute configuration of N,N‐dimethyl‐3‐(naphthalen‐2‐yl)‐butan‐1‐amines: Potential sigma1 ligands

et al. 2006

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We describe the preparation of racemic N,N-dimethyl-3-(naphthalen-2-yl)-butan-1-amines, potential sigma1 ligands, and their resolution via chiral HPLC. In order to obtain enantiopure compounds, direct chromatographic methods of separation using chiral stationary phases were investigated. Different methods suitable for both analytical and semipreparative purposes are proposed. The best resolutions were achieved using cellulose tris (3,5-dimethylphenyl carbamate) (Chiralcel OD and OD-H) and amylose tris (3,5-dimethylphenyl carbamate) (Chiralpak AD). On the basis of the preliminary chromatographic results, the resolution of compound 1 was transferred onto a Chiralcel OD semipreparative column. The enantiomers were obtained in high enantiomeric excess. The configurational assignment was performed by circular dichroism. Computational analysis was used to explore the enantioselective recognition process of compound 1 with the Chiralcel OD stationary phase.

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Computational studies on chiral discrimination mechanism of cellulose trisphenylcarbamate

Cited by 90 publications

References 28 publications

Polysaccharide Derivatives for Chromatographic Separation of Enantiomers

Polysaccharide Derivatives for Chromatographic Separation of Enantiomers

Comparison of cyclodextrin-barbiturate noncovalent complexes using electrospray ionization mass spectrometry and capillary electrophoresis

Enantioselective chromatography and absolute configuration of N,N‐dimethyl‐3‐(naphthalen‐2‐yl)‐butan‐1‐amines: Potential sigma1 ligands

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