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

• Bulletin of the Korean Chemical Society
• /
• v.28 no.12
• /
• pp.2435-2441
• /
• 2007

The catalytic enantioselective electrophilic fluorinations of active methane compounds promoted chiral palladium complexes have been developed. Treatment of α-cyano acetates and α-cyanoalkylphosphonates with N-fluorobenzenesulfonimide as the fluorine source under mild reaction conditions afforded the corresponding α-cyano-α-fluorinated adducts in high yields with excellent enantiomeric excesses (up to 99% ee). These reactions can be conducted in alcoholic solvents without any precaution to exclude water and moisture.

• Bulletin of the Korean Chemical Society
• /
• v.30 no.4
• /
• pp.829-836
• /
• 2009

The catalytic enantioselective electrophilic fluorinations of active methine compounds promoted chiral palladium complexes have been developed. Treatment of $\beta$-keto phosphonates and $\beta$-ketoesters with N-fluorobenzenesulfonimide as the fluorine source under mild reaction conditions afforded the corresponding $\alpha$-fluorinated adducts in high yields with excellent enantiomeric excesses (up to 99% ee). These reactions can be conducted in alcoholic solvents without any precaution to exclude water and moisture.

• KSBB Journal
• /
• v.17 no.4
• /
• pp.321-325
• /
• 2002

Chiral epoxides are valuable intermediates for the asymmetric synthesis of enantiopure bioactive compounds. Microbial epoxide hydrolases (EHs) are newly discovered enzymes and versatile biocatalysts for the preparation of chiral epoxides by enantioselective hydrolysis of cheap and easily available racemic epoxide substrates. EHs are commercially potential biocatalysts due to their characteristics such as high enantioselectivity, cofactor-independent catalysis, and easy-to-Prepare catalysts. In this Paper, recent progresses in biochemistry and molecular biology of EH and developments of novel reaction systems are reviewed to evaluate the commercial feasibility of EH-catalyzed hydrolytic kinetic resolution for the production of chiral epoxides.

• Journal of Life Science
• /
• v.16 no.1
• /
• pp.168-174
• /
• 2006

Enantiopure epoxides are valuable intermediates for the asymmetric synthesis of enantiopure bioactive compounds. Microbial epoxide hydrolases (EHs) are versatile biocatalysts for the preparation of enantiopure epoxides by enantioselective hydrolysis of cheap and easily available racemic epoxide substrates. EHs are commercially potential biocatalysts due to their characteristics such as high enantioselectivity, cofactor-independent catalysis, and easy-to-prepare catalysts. In this paper, recent progresses In molecular engineering of EHs are reviewed to evaluate the commercial feasibility of EH-catalyzed hydrolytic kinetic resolution for the production of enantiopure epoxides.

• Applied Chemistry for Engineering
• /
• v.27 no.5
• /
• pp.490-494
• /
• 2016

This paper describes the very efficient and highly enantioselective ring opening of terminal epoxides with alkyl and arene sulfonic acid. The dinuclear chiral (salen) Co complexes bearing Lewis acids of Al, Ga and In catalyze the reaction enantioselectively in the presence of tetrabutylammonium chloride using tert-butyl methyl ether as a solvent. The variation of the anion of the tetra butyl ammonium salt has significant impact on the reactivity and selectivity of the asymmetric ring opening of phenyl glycidyl ether with p-toluenesulfonic acid. The order of reactivity and selectivity was found to be $Cl^-$ > $l^-$ > $Br^-$ > $OH^-$. Strong synergistic effects of the different Lewis acid centers of Co-Al, Co-Ga and Co-In complexes were observed in the catalytic process. The dinuclear chiral salen catalyst containing $AlCl_3$ was found to be most active and highly enantioselective (91% ee).

• Bulletin of the Korean Chemical Society
• /
• v.30 no.5
• /
• pp.1047-1053
• /
• 2009

The future use of hydrogen as an energy source is expected to increase on account of its environmentally friendliness. In order to enhance the production of hydrogen, Pd ions (0.01, 0.05, 0.1, and 0.5 mol%) were incorporated $TiO_2$ (Pd-$TiO_2$) and used as a photocatalyst. The UV-visible absorbance decreased with increasing level of palladium incorporation without a wavelength shift. Although all the absorption plots showed excitation characteristics, there was an asymmetric tail observed towards a higher wavelength caused by scattering. However, the intensity of the photoluminescence (PL) curves of Pd-$TiO_2$ was smaller, with the smallest case being observed at 0.1 and 0.5 mol% Pd-$TiO_2$, which was attributedto recombination between the excited electrons and holes. Based on these optical characteristics, the evolution of $H_2$ from methanol/water (1:1) photo-splitting over Pd-$TiO_2$ in the liquid system was enhanced, compared with that over pure $TiO_2$. In particular, 2.4 mL of $H_2$ gas was produced after 8 h when 0.5 g of a 1.0 mol% Pd-$TiO_2$ catalyst was used. $H_2$ was stably evolved even after 28 h without catalytic deactivation, and the amount of $H_2$ produced reached 14.5 mL after 28 h. This is in contrast to the case of the Pd 0.1 mol% impregnated $TiO_2$ of $H_2$ evolution of 17.5 mL due to the more decreasedelectron-hole recombination.

• Journal of the Korean Vacuum Society
• /
• v.17 no.1
• /
• pp.51-57
• /
• 2008

we have demonstrated structural evolution and optical properties of Si-nanowires (NWs) synthesized on Si (111) substrates with nanoscale Au-Si islands by rapid thermal chemical vapor deposition (RTCVD). The Au-Si nano-islands (10-50nm in diameter) were employed as a liquid-droplet catalysis to grow Si-NWs via vapor-liquid-solid mechanism. The Si-NWs were grown by a mixture gas of SiH4 and H2 at a pressure of 1.0 Torr and temperatures of $500{\sim}600^{\circ}C$. Scanning electron microscopy measurements showed that the Si-NWs are uniformly sized and vertically well-aligned along <111> direction on Si (111) surfaces. The resulting NWs are ${\sim}60nm$ in average diameter and ${\sim}5um$ in average length. High resolution transmission microscopy measurements indicated that the NWs are single crystals covered with amorphous SiOx layers of ${\sim}3nm$ thickness. In addition, the optical properties of the NWs were investigated by micro-Raman spectroscopy. The downshift and asymmetric broadening of the Si main optical phonon peak were observed in Raman spectra of Si-NWs, which indicates a minute stress effects on Raman spectra due to a slight lattice distortion led by lattice expansion of Si-NW structures.

• Journal of the Korean Vacuum Society
• /
• v.16 no.4
• /
• pp.279-285
• /
• 2007

We have demonstrated structural evolution and optical properties of the Si-NWs on Si (111) substrates with synthesized nanoscale Au-Si islands by rapid thermal chemical vapor deposition(RTCVD). Au nano-islands (10-50nm in diameter) were employed as a liquid-droplet catalysis to grow Si-NWs via vapor-liquid-solid mechanism. Si-NWs were grown by a mixture gas of $SiH_4\;and\;H_2$ at pressures of $0.1{\sim}1.0$Torr and temperatures of $450{\sim}650^{\circ}C$. SEM measurements showed the formation of Si-NWs well-aligned vertically for Si (111) surfaces. The resulting NWs are 30-100nm in diameter and $0.4{\sim}12um$ in length depending on growth conditions. HR-TEM measurements indicated that Si-NWs are single crystals convered with about 3nm thick layers of amorphous oxide. In addition, optical properties of NWs were investigated by micro-Raman spectroscopy. The downshift and asymmetric broadening of the Si optical phonon peak with a shoulder at $480cm^{-1}$ were observed in Raman spectra of Si-NWs.