• Journal of the Korean Chemical Society
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• v.61 no.5
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• pp.244-250
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• 2017

Reduction of (${\pm}$)-3-ketoproline ethyl ester (1) by $NaBH_4$ in the presence of $CaCl_2$ and $MgCl_2$ as the chelating agents gave selective products cis-3(R/S)-alcohols, while reduction by $NaBH_4$ alone or chelated with $NiCl_2$ and $AlBr_3$ gave mixtures of cis- and trans-alcohols. The reduction of (${\pm}$)-1 by various vegetables however, gave exclusively the cis-alcohol as the major and trans-alcohol as the minor. On the contrary, reduction of (${\pm}$)-1 by carrot afforded a mixture of cis- and trans-alcohols, in which the trans-alcohol exists as the major product. In addition, we found that this biocatalyst selectively converted S-enantiomer of (${\pm}$)-1 to the cis-alcohol, and R-enantiomer to a mixture of cis- and trans-alcohols with cis-alcohol as the major product. This fact prompted us to use various fresh plant tissues for stereoselective reduction of diverse types of pyrrolidinones, as its stereoselectivity towards racemic mixtures is higher compared to that using chemical reducing agents.

• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.125-130
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• 1992

Stereoisomers of trifluoroethylmandelate(mandelic acid trifluoroethylester) were synthesized from each isomer of mandelic acid and trifluoroethanol with p-toluene sulfonic acid in order to study the enantioselectivity of lipase in organic solvent. The products were identified by $^1H$ NMR and elemental analysis and their physical properties such as melting point, densities and specific optical rotations($[{\alpha}]_{25}{^D}$) were also characterized. $[{\alpha}]_{25}{^D}$ of (+)- and (-)-trifluoroethylmandelate were +74° and -75.4°, respectively. The trifluoroethylmandelate was found out to be as a good substrate for the transesterfication stereoselectivity of lipases in organic solvent. Any significant difference of the lipase catalyzed transesterification activity between (+)- and (-)-methylchloropropionate was not found, and even lipase activity of transesterfication was not found with high optical polar (+)-and (-)-methylmandelate.

• Journal of Microbiology and Biotechnology
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• v.24 no.7
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• pp.936-942
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• 2014

Using racemic (R,S)-2-(4-chlorophenyl)-3-methylbutyramide, an intermediate for the chiral pyrethroid insecticide Esfenvalerate, as a sole nitrogen source in a minimal medium, several strains with high enatioselectivity (${\geq}98%$) were isolated by enrichment techniques. One of the strains, LG 31-3, was identified as Burkholderia multivorans, based on physiological and morphological tests by a standardized Biolog station for carbon source utilization. A novel amidase was purified from B. mutivorans LG 31-3 and characterized. The enzyme exhibited (S)-selective amidase activity on racemic (R,S)-2-(4-chlorophenyl)-3-methylbutyramide. Addition of the racemic amide induced the production of the enantioselective amidase. The molecular mass of the amidase on SDS-PAGE analysis was shown to be 50 kDa. The purified amidase was subjected to proteolytic digestion with a modified trypsin. The N-terminal and internal amino acid sequences of the purified amidase showed a high sequence homology with those deduced from a gene named YP_366732.1 encoding indole acetimide hydrolase from Burkholderia sp. 383.

• Journal of the Korean Chemical Society
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• v.55 no.2
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• pp.251-255
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• 2011

A new and highly stereoselective synthesis of (E)-4'-amino-3,4,5-trimethoxystilbene was achieved by using 3,4,5-trimethoxybenzaldehyde and p-nitrotoluene as starting materials through condensation under solvent-free condition and followed by the reducing of nitro group with the system of $NH_2NH_2/FeCl_3$/C in ethanol. The crystal structure of (E)-4'-amino-3,4,5-trimethoxystilbene was also determined by X-ray diffraction analysis.

• Bulletin of the Korean Chemical Society
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• v.10 no.1
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• pp.75-80
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• 1989

The approximate rates and stoichiometry of the reaction of excess potassium 9-sec-amyl-9-boratabicylco[3.3.1]nonane (K 9-sec-Am-9-BBNH) with selected organic compounds containing representative functional goups under standardized conditions (tetrahydrofuran, $0^{\circ}C)$ were examined in order to explore the reducing characteristics of the reagent for selective reductions. The reagent readily reduces aldehydes, ketones, acid chlorides and epoxides to the corresponding alcohols. However, carboxylic acid, aliphatic nitriles, t-amides, and some sulfur compounds show very little reactivity or no reactivity to this reagent. The most interesting feature of the reagent is that aromatic nitriles are reduced moderately to the corresponding aldehyde stage, wheras aliphatic nitriles are inert. In addition, the reagent shows a high stereoselectivity toward cyclic ketones at $0^{\circ}C$ and - $25^{\circ}C.$ The selectivity exhibited at $0^{\circ}C$ is comparable to that by lithium trisiamylborohydride at that temperature.

• Bulletin of the Korean Chemical Society
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• v.9 no.3
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• pp.149-152
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• 1988

A mixture of (Z,Z)-3,13-octadecadien-1-yl acetate(1) and its (E,Z)-isomer(2), the sex pheromone of the cherry tree borer, Synanthedon hector Butler was synthesized. (Z)-11-Octadecen-1-al(3) was prepared from 1,10-decandiol. The Wittig reaction the above aldehyde3 with carboethoxymethylenetriphenylphosphorane, or the Wadsworth-Emmons reaction of the above aldehyde3 with the anion of triethylphosphonoacetate gave ethyl (Z,Z)-2,13-octadecadienoate and its (E,Z)-isomer. Deconjugative protonation of ethyl (Z,Z)-2,13-octadecadienoate and its (E,Z)-isomer with potassium hexamethyldisilazide followed by aqueous ammonium chloride work-up afforded stereoselectiv디y ethyl (E,Z)-3,13-octadecadienoate and its (Z,Z)-isomer, respectively, of which stereoselectivity was adjusted to give the product in the required ratio. Exposure of the above deconjugated ester to excess lithium aluminium hydride resulted in formation of the penultimate (Z,Z)-3,13-octadecadien-1-ol and its (E,Z)-isomer. Acetylation of the desired alcohols afford the final products, (Z,Z)-3,13-octadecadien-1-yl acetate(1) and its (E,Z)-isomer(2).

• Journal of the Korean Chemical Society
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• v.31 no.2
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• pp.133-142
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• 1987

Stereoselectivities of (4+2) cycloaddition reactions of cyclopentadiene with the methyl-substituted allenic acids and esters were investigated by application of $\pi$-nonbonded interaction ($\pi$-NBI) theory. 2-FMO method has been found to be adequate for determination of endo selectivities of diene(LUMO)-dienophile (LUMO) interaction in the thermal reactions and diene (HOMO)-dienophile (LUMO) interaction in the Lewis acid catalyzed reactions. $\pi$-isoconjugate diene structure was formed by through-bond interaction of allene moiety with methyl group in the cumulated diene system; the methyl substituent acts as a conjugative chain and causes inter-level narrowing effect of the FMO's. In dienophiles which do not form $\pi$-isoconjugate diene system, methyl group acts merely as an electron donating group. In thermal reactions, the stereoselectivities are controlled by $\pi$-nonbonded secondary orbital interaction ($\pi$-NSOI) of methyl substituent, which behaves similarly as an ethylene molecule.

• Biomedical Science Letters
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• v.8 no.4
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• pp.211-215
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• 2002

The baculovirus/Sf9 cell expression can be employed as a powerful system for producing large amounts of the human erythrocyte glucose transporter, GLUT1 heterologously In order to exploit the system further, it is necessary to develop a convenient method for demonstrating that the transporter expressed in insect cells is biologically active. To achieve this, we have expressed the human CLUT1 in insect cells and photolabelled the expressed protein with [$^3$H] cytochalasin B, a potent inhibitor of the human erythrocyte glucose transporter. Subsequently, the labelled proteins were analysed by SDS-polyacrylamide gel electrophoresis (SDS-PAGE). Membranes labelled with [$^3$H] cytochalasln B in the presence of L-Glucose yielded a single sharp peak of labelling of apparent $M_r$ 45,000 on SDS/polyacrylamide gels. The mobility of this peak corresponded exactly to that of the band detected by anti-glucose transporter antibodies on Western blots of membranes prepared from insect cells infected with recombinant virus. In addition, the sharpness of the radioactive peak provides further evidence for the conclusion that the expressed protein is much less heavily and heterogeneously glycosylated than its erythrocyte counterpart. No peak of labelling was seen with the membranes prepared from non-infected Sf9 cells. Furthermore, the incorporation of label into this peak was completely inhibited by the presence of 500 mM-D-Glucose during tile photolabelling procedure, showing the stereoselectivity of the labelling. These evidences clearly show that human glucose transporter expressed in insect cells exhibits native-like biological activity, and that photolabelling with [$^3$H] cytochalasin B can be a convenient means for analysing the biological activity of the transport protein expressed in insect cells.

• Journal of the Korean Chemical Society
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• v.35 no.5
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• pp.500-505
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• 1991

The stereoselectivity on the electron-transfer reaction between optical active ${\bigwedge}$-[CO(EDDS)]- and conformationally restricted complex $[Co({\pm}chxn)_3]^{2+}$ has been examined in aqueous solution. The products are four conformational isomers $(lel_3,\;lel_2ob,\;lelob_2,\;and\;ob_3)$ of ${\bigwedge}$-[Co(chxn)$_3]^{3+}$ with optical purities of 22% e.e, 25% e.e, 11% e.e, and 10% e.e, respectively. The reaction between ${\bigwedge}$-[CO(EDDS)]- and $[Co({\pm}chxn)_3]^{2+}$ in DMSO produced lel3-${\Delta}$ and lel2ob-${\Delta}$-[Co(chxn)$_3]^{3+}$ whose optical purities are 100% e.e, and 75% e.e, respectively.

• Bulletin of the Korean Chemical Society
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• v.15 no.2
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• pp.132-138
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• 1994

Bis(diethylamino)aluminum hydride was utilized in a systematic study of the approximate rates and stoichiometry of the reaction of excess reagent with 55 selected organic compounds containing representative functional groups under standardized conditions (THF, $0^{\circ}C$, reagent to compound=4 : 1) in order to define the characteristics of the reagent for selective reductions. The reducing action of BEAH was also compared with that of the parent aluminum hydride. The reducing action of the reagent is quite similar to that of aluminum hydride, but the reducing power is much weaker. Aldehydes and ketones were readily reduced in 1-3 h to the corresponding alcohols. However, unexpectedly, a ready involvement of the double bond in cinnamaldehyde was realized to afford hydrocinnamyl alcohol. The introduction of diethylamino group to the parent aluminum hydride appears not to be appreciably influential in stereoselectivity on the reduction of cyclic ketones. Both p-benzoquinone and anthraquinone utilized 2 equiv of hydride readily without evolution of hydrogen, proceeded cleanly to the 1,4-reduction products. Carboxylic acids and acid chlorides underwent reduction to alcohols slowly, whereas cyclic anhydrides utilized only 2 equiv of hydride slowly to the corresponding hydroxylacids. Especially, benzoic acid with a limiting amount of hydride was reduced to benzaldehyde in a yield of 80%. Esters and lactones were also readily reduced to alcohols. Epoxides examined all reacted slowly to give the ring-opened products. Primary and tertiary amides utilized 1 equiv of hydride fast and further hydride utilization was quite slow. The examination for possibility of achieving a partial reduction to aldehydes was also performed. Among them, benzamide and N,N-dimethylbenzamide gave ca, 90% yields of benzaldehyde. Both the nitriles examined were also slowly reduced to the amines. Unexpectedly, both aliphatic and aromatic nitro compounds proved to be relatively reactive to the reagent. On the other hand, azo- and azoxybenzenes were quite inert to BEAH. Cyclohexanone oxime liberated 1 equiv of hydrogen and utilized 1 equiv of hydride for reduction, corresponding to N-hydroxycyclohexylamine. Pyridine ring compounds were also slowly attacked. Disulfides were readily reduced with hydrogen evolution to the thiols, and dimethyl sulfoxide and diphenyl sulfone were also rapidly reduced to the sulfides.