Chiral discrimination controlled by the solvent dielectric constant

Sakai, Kenichi; Sakurai, Rumiko; Hirayama, Noriaki

doi:10.1016/j.tetasy.2004.02.015

Cited by 46 publications

(29 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…A very similar behaviour was observed for 2,7-bis(trifluoromethyl)tricyclo[4.3.1.1 3,8 ]-undecanesyn-2,syn-7-diol [18] and cyclo-bis(2-amino-7-cyano-4-methoxyindan-2-carboxylic) acid [19]. It is very likely that the polarity of solvent influences the racemic resolution process which was observed in other cases [20,21]. The central 1,2,4-triazole ring of (I) is substituted at the C3, N4 and C5 atoms by 2-cyclohexanecarboxylic acid, phenyl and 2-pyridyl groups, respectively.…”

Section: Resultssupporting

confidence: 72%

2-(4-Phenyl-5-pyridin-2-yl-4H-1,2,4-triazol-3-yl)cyclohexanecarboxylic Acid and Its DMSO Solvate: Synthesis, Crystal Structure and Biological Activity

Mazur

Kozioł

Modzelewska-Banachiewicz

et al. 2011

J Chem Crystallogr

View full text Add to dashboard Cite

A new 1,2,4-triazole derivative, 2-(4-phenyl-5-pyridin-2-yl-4H-1,2,4-triazol-3-yl)cyclohexanecarboxylic acid, C 20 H 20 N 4 O 2 (I), and its dimethyl sulfoxide solvate 1:1 (II) have been synthesized and their crystal structure was established. Compound (I) was screened for its antiproliferative and antiinflammatory activity. Structural analysis indicated the substantial difference between two symmetry independent molecules in (I) and this in (II), it manifests in the relative orientation of pyridine/phenyl and triazole rings, as well as in the orientation of carboxyl group with respect to cyclohexane ring. The molecules A and B in the crystal (I) form two hydrogen-bonded chains through O-H carboxyl and N triazole atoms, giving separate catemers of symmetry independent molecules. The catemer of (IA) running along the 2 1 axis is homochiral, while the catemer (IB) is racemic-formed about the c glide plane. In the crystalline solvate (II) complexation of (I) with DMSO induced enantiomeric self-resolution. Obtained crystals are racemic twins, in which each part is built of one enantiomer of (I) having the relative configuration 11S,12R or 11R,12S. A pair of host-guest molecules is linked by the O-H carboxyl _O DMSO hydrogen bond.

show abstract

Section: Resultssupporting

confidence: 72%

2-(4-Phenyl-5-pyridin-2-yl-4H-1,2,4-triazol-3-yl)cyclohexanecarboxylic Acid and Its DMSO Solvate: Synthesis, Crystal Structure and Biological Activity

Mazur

Kozioł

Modzelewska-Banachiewicz

et al. 2011

J Chem Crystallogr

View full text Add to dashboard Cite

show abstract

“…However, the salt of the antipode (R)-AC crystallized when the solvent was in meium polarity (29<ε<58). 46,47,48 …”

Section: Influence Of Dielectric Constantmentioning

confidence: 99%

Separation of the Mixtures of Chiral Compounds by Crystallization

Pálovics¹,

Faigl²,

Fogassy³

2012

Advances in Crystallization Processes

View full text Add to dashboard Cite

“…In the resolution process of (RS)-α-amino-ε-caprolactam(ACL) with N-tosyl-(S)-phenylalanine(TPA), high optical yields for (R)-and (S)-ACL can be attained only by adjusting the dielectric constants (ε) of the solvents employed [2,3]. The results of a series of resolution experiments obtained for the (RS)-ACL : (S)-TPA system in various solvent systems are given in Table 1.…”

Section: (Rs)-α-amino-ε-caprolactam: N-tosyl-(s)-phenylalanine Systemmentioning

confidence: 99%

“…In the process of our studies we have recently discovered a typical example of a drastic effect of solvent on chiral resolution [2,3]. In this particular resolution system, chiral discrimination is controlled by the dielectric properties of the solvents used.…”

Section: Introductionmentioning

confidence: 96%

Molecular Mechanisms of Dielectrically Controlled Resolution (DCR)

Sakai

Sakurai

Hirayama

2006

Topics in Current Chemistry

Self Cite

View full text Add to dashboard Cite

It is widely believed that the chiral discrimination process is solely dependent on the stereochemistryof the relevant molecules. However, through systematic studies on several resolution systems with popularchiral selectors, we have discovered a new fact that triggers modification of this prevailing conceptof chiral resolution. The studies have demonstrated that one enantiomer of a chiral selector can recognizeboth enantiomers of a target molecule in different solvent systems with different dielectric constants.The phenomenon was termed dielectrically controlled resolution (DCR). Since DCR was observed in differentresolution systems and was not too specific to a particular system, DCR was expected to widely occurin various resolution systems. We have investigated the molecular mechanism underlying this interestingphenomenon based on X-ray analysis of the relevant diastereomeric salts. The disclosed mechanism clearlyindicates that a chiral selector can inherently recognize both enantiomers of a target moleculeand only the dielectric property of the solvent employed in the resolution process governs the selectionof the enantiomer.

show abstract

Chiral discrimination controlled by the solvent dielectric constant

Cited by 46 publications

References 3 publications

2-(4-Phenyl-5-pyridin-2-yl-4H-1,2,4-triazol-3-yl)cyclohexanecarboxylic Acid and Its DMSO Solvate: Synthesis, Crystal Structure and Biological Activity

2-(4-Phenyl-5-pyridin-2-yl-4H-1,2,4-triazol-3-yl)cyclohexanecarboxylic Acid and Its DMSO Solvate: Synthesis, Crystal Structure and Biological Activity

Separation of the Mixtures of Chiral Compounds by Crystallization

Molecular Mechanisms of Dielectrically Controlled Resolution (DCR)

Contact Info

Product

Resources

About