• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1590-1600
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• 2014

Cinchona-based bifunctional catalysts have been extensively employed in the field of organocatalysis due to the incorporation of both hydrogen-bonding acceptors (quinuclidine) and hydrogen-bonding donors (e.g., alcohol, amide, (thio)urea and squaramide) in the molecule, which can simultaneously activate nucleophiles and electrophiles, respectively. Among them, cinchona-derived (thio)urea and squaramide catalysts have shown remarkable application potential by using their bifurcated hydrogen bonding donors in activating electrophilic carbonyls and imines. However, due to their bifunctional nature, they tend to aggregate via inter- and intramolecular acid-base interactions under certain conditions, which can lead to a decrease in the enantioselectivity of the reaction. To overcome this self-aggregation problem of bifunctional organocatalysts, we have successfully developed a series of sulfonamide-based organocatalysts, which do not aggregate under conventional reaction conditions. Herein, we summarize the recent applications of our cinchona-derived sulfonamide organocatalysts in highly enantioselective methanolytic desymmetrization and decarboxylative aldol reactions. Immobilization of sulfonamide-based catalysts onto solid supports allowed for unprecedented practical applications in the synthesis of valuable bioactive synthons with excellent enantioselectivities.

• 한국생물공학회:학술대회논문집
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• 2000.11a
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• pp.593-596
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• 2000

Chiral epoxides are useful chiral synthons in organic synthesis and various biological methods have been investigated for the production of chiral epoxides. In this work, enantioselective resolution of racemic styrene oxide was investigated using an isolated Aspergillus niger sp. for the production of optically pure (S) -styrene oxide. The enantioselectivity and initial hydrolysis rates of racemic substrate were highly dependent on the pH, temperature, and the volume ratio of cosolvent. The experimental sets of pH, temperature, and the volume ratio of cosolvent were designed using central composite experimental design, and the reaction conditions were optimized using response surface analysis. The optimal conditions of pH, temperature, and the volume ration of cosolvent were determined to be 7.78, $28.32^{\circ}C$, and 2.4 %(v/v), respectively, and optically pure (S)-styrene oxide (> 99% ee) could be obtained with the 35 % yield by microbial enantioselective hydrolysis reaction.

• Biotechnology and Bioprocess Engineering:BBE
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• v.8 no.5
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• pp.306-308
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• 2003

Enantioselective hydrolysis for the production of chiral styrene oxide was investigated using the epoxide hydrolase activity of a newly isolated Rhodosporidium kratochvilovae SYU-08. The effects of reaction parameters - buffer type, pH, temperature, initial substrate concentrations, phenyl-1,2-ethanediol concentrations on hydrolysis rate, and enantioselectivity - were analyzed. Optically active (S)-styrene oxide with an enantiomeric excess higher than 99 % was obtained from its racemate. with a yield of 38 % (theoretically 50% maximum yield) from an initial concentration of 80 mM.

• Biomolecules & Therapeutics
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• v.4 no.3
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• pp.209-223
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• 1996

Chirality is important in the context of biological activity because at a molecular level, asymmetry dominates biological process. While most pharmaceuticals of natural origin are single enantiomers, most of the synthesized chiral drugs are used in the form of racemic mixtures of two or more diastereomers. The enantiomers of a racemic drug generally differ in pharmacodynamic and pharmacokinetic properties as a consequence of stereoselective interaction with optically active molecular components of living organism. In pharmacokinetics and pharmacodynamics enantioselectivity plays an important role. The information on the sum of eutomer and distorter in a racemic drugs is very important in the estimation of therapeutic advantage and/or toxicity of racemates. The choice of preferentially developing a single enantiomer should be based on actual therapeutic advantages and especially improved safety.

• Bulletin of the Korean Chemical Society
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• v.31 no.1
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• pp.82-86
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• 2010

Quinine (QN) is a weak anion-exchange type chiral selector and QN-based silica stationary phases have been widely used for enantioseparation of acidic chiral analytes in HPLC and recently in CEC. In this work we report enantioseparation of non-acidic chiral analytes on a quinine carbamate-immobilized zirconia (QNZ) in reversed-phase (RP) CEC. Influences of pH, composition of the buffer, acetonitrile content and the applied voltage on enantioseparation were examined. Enantiomers of the analytes investigated are well separated in acetonitrile/phosphate buffer mobile phases. Separation data on QNZ were compared to those on QN-bonded silica (QNS). Retention was longer but better enantioselectivity and resolution were obtained on QNZ than QNS.

• 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.10
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• pp.2973-2979
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• 2010

The newly synthesized homogeneous chiral Co(III) salen complexes were anchored non-covalently on the acidic sites of mesoporous Al-SBA-15. The Bronsted and Lewis acidic sites are attributed to the immobilization of fluorine functionalized chiral salen complexes on the supports. XRD, BET, TEM, FT-IR and ESCA (XPS) analyses were performed to characterize the property of support, and the structure of new homogeneous and heterogeneous chiral Co salen catalyst. The homogeneous and heterogeneous catalysts could be applied in asymmetric ring opening of epichlorohydrine (ECH) by water. They showed very high enantioselectivity and a good yield up to 99% in the catalytic synthesis of optically active products.

• Bulletin of the Korean Chemical Society
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• v.30 no.8
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• pp.1771-1777
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• 2009

The homogeneous B$F_3$ containing chiral Co(III) salen complexes were anchored non-covalently on the surfaces of mesoporous SBA-16 silica containing aluminum species. The Brönsted and Lewis acidic sites are attributed to the immobilization of fluorine functionalized chiral salen complexes on the supports. The FT-IR, UV, ESCA, and NMR analyses were performed to determine the structure of synthesized chiral salen catalysts. These heterogeneous catalysts could be applied in asymmetric ring opening of terminal epoxides by water and phenol derivatives. They showed very high enantioselectivity and yield more than 98% in the catalytic synthesis of optically active products.

• Bulletin of the Korean Chemical Society
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• v.30 no.2
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• pp.389-396
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• 2009

MFI structural zeolite (ZSM-5 or Sililcalite) was treated with HF solution to introduce mesoporous channels in the microporous crystals. Inner mesopore size could be controlled from 2.5 to 3.5 nm by changing the concentration of HF solution. The pore structure of HF-treated MFI zeolite was studied by instrumental analysis. The active Co (III) salen complex monomers were successfully anchored non-covalently on the surfaces of mesoporous MFI-type zeolite. These heterogeneous catalysts could be applied in asymmetric ring opening of terminal epoxides by phenol derivatives. It showed very high enantioselectivity and yield up to 95% in the catalytic synthesis of optically active $\alpha$-aryloxy alcohol compounds.

• Bulletin of the Korean Chemical Society
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• v.24 no.7
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• pp.911-915
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• 2003

Two liquid chromatographic chiral stationary phases (CSPs) based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid were successfully applied in the resolution of racemic tocainide and its analogues. In the resolution of tocainide, especially, the CSP containing N-CH₃ amide tethering groups was quite effective, showing clear baseline resolution (RS: 2.66) with reasonable enantioselectivity ( a: 1.25). Consequently, the CSP containing N-CH₃ amide tethering groups is expected to be useful to monitor the enantiomeric composition of tocainide in clinical samples. In addition, the chromatographic behaviors for the resolution of tocainide and its analogues on the two CSPs were found controllable by varying the content and the type of organic and acidic modifiers in aqueous mobile phase.