• Journal of Microbiology and Biotechnology
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• v.29 no.11
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• pp.1769-1776
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• 2019

Ethyl (S)-3-hydroxy-3-(2-thienyl) propanoate ((S)-HEES) acts as a key chiral intermediate for the blockbuster antidepressant drug duloxetine, which can be achieved via the stereoselective bioreduction of ethyl 3-oxo-3-(2-thienyl) propanoate (KEES) that contains a 3-oxoacyl structure. The sequences of the short-chain dehydrogenase/reductases from Chryseobacterium sp. CA49 were analyzed, and the putative 3-oxoacyl-acyl-carrier-protein reductase, ChKRED12, was able to stereoselectively catalyze the NADPH-dependent reduction to produce (S)-HEES. The reductase activity of ChKRED12 towards other substrates with 3-oxoacyl structure were confirmed with excellent stereoselectivity (>99% enantiomeric excess) in most cases. When coupled with a cofactor recycling system using glucose dehydrogenase, the ChKRED12 was able to catalyze the complete conversion of 100 g/l KEES within 12 h, yielding the enantiopure product with >99% ee, showing a remarkable potential to produce (S)-HEES.

• Proceedings of the Ginseng society Conference
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• 1993.09a
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• pp.74-83
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• 1993

In an attempt toward the synthesis of the difficulty accessible ginseng saponins the four dammarane glycosides identical to the natural $ginsenosides-Rh_2,$ - F2, compound K and chikusetsusaponin - LT8 have been prepared from betulafolienetriol(=dammar-24-ene-$3{\alpha},12{\beta}\;20(S)-triol).\;3-O-{\beta}-D-Glucopyranoside$ of 20(S) - protopanaxadiol $(=ginsenoside-Rh_2)$ have been obtained by the regio - and stereoselective glycosylation of the $12-O-acetyldammar-24-ene-3{\beta},\;12{\beta},$ 20(S)-triol. The 12-ketoderivative of 20(S)-protopanaxadiol has been used as aglycon in synthesis of chikusetsusaponin - LT8. Attempted regio - and stereoselective glycosylation of the less reactive tertiary C - 20 - hydroxyl group in order to synthesize the $20-O-{\beta}-D-glucopyranoside$ of 20(S)-protopanaxadiol(=compound K) using 3, 12 - di - O - acetyldammar - 24 - ene - $3{\beta},12{\beta},20(S)$-trial as aglycon was unsuccessful. Glycosylation of 3, 12 - diketone of betulafolienetriol followed by $NaBH_4$ reduction yielded the $20-O-{\beta}-D-glucopyranoside\;of\;dammar-24-ene-3{\beta},12{\alpha},$ 20(S)-triol, the $12{\alpha}-epimer$ of 20(S) - protopanaxadiol. Moreover, a number of semisynthetic ocotillol - type glucosides, analogs of natural pseudoginsenosides, have been prepared.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.367-367
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• 2010

The adsorption configurations of S-proline on Ge(100) were studied using scanning tunneling microscopy (STM), density functional theory (DFT) calculations, and high-resolution core-level photoemission spectroscopy (HRCLPES). We identified three adsorption structures of S-proline on Ge(100) through analysis of the STM images, DFT calculations, and HRCLPES results: (i) an 'intrarow O - H dissociated and N dative bonded structure', (ii) an 'O - H dissociation structure', and (iii) an 'N dative bonded structure'. Moreover, because adsorption through the N atom of S-proline produces a new chiral center due to symmetry reduction by N dative bonding, the adsorption configurations have either (R,S) or (S,S) chirality, yielding an (R,S)-'intrarow O - H dissociated and N dative bonded structure' and an (R,S)-'N dative bonded structure', with a preference for reaction at the Re face. This work presents a novel method for generating stereoselective attachment using S-proline molecules adsorbed onto a Ge(100) surface.

• Bulletin of the Korean Chemical Society
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• v.19 no.2
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• pp.236-242
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• 1998

Reaction of carbonyl compounds with Al-alkoxydiisobutylalane (DIBAOR, R=H, Et, i-Pr, t-Bu) has been investigated in detail so as to establish their usefulness as selective reducing agents in organic synthesis. The reagents appear to be extremely mild and can reduce only aldehydes and ketones effectively under mild conditions. All the other common organic functional groups are not affected by these reagents. The reagents can also reduce α,β-unsaturated aldehydes and ketones to the corresponding allylic alcohols without any detectable 1,4-reduction. Furthermore, the reagents show a highly chemoselective discrimination between aldehyde and ketone, between aldehydes, and between ketones. Even more remarkable is the stereoselective reduction of cyclic ketones to the thermodynamically more stable alcohol epimers.

• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.307-309
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• 1990

The stereoselectivity of the reaction between methyl vinyl ketone dimer, which contains two possible sites of chelation, and zinc borohydride or diisobutylaluminum hydride has been studied in order to illuminate the factors involved in the high levels of asymmetric induction obtained in the bicyclic system. The conditions for the formation of the exo-5,7-dimethyl-6,8-dioxabicyclo[3.2.1]octane are DIBAH reduction of MVK dimer in ether at reflux followed by acidic cyclizatioan, and for the endo isomer are $Zn(BH_4)_2$ reduction with $ZnCl_2$ at $0^{\circ}C.$.

• Bulletin of the Korean Chemical Society
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• v.7 no.1
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• pp.66-69
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• 1986

The reaction of potassium trialkoxyborohydrides of varying steric requirements with lithium chloride in tetrahydrofuran(THF) was examined in detail to establish the generality of this synthesis of the corresponding lithium trialkoxyborohydrides. The metal ion exchange reaction between potassium triisopropoxyborohydride and lithium chloride in THF proceeded instantly at room temperature and the corresponding lithium salt was very stable toward disproportionation. However, for R = s-Bu, t-Bu and 2-methylcyclohexyl, with increasing steric requirement, the lithium derivatives were unstable and thus dissociated into $(RO)BH_3^-\;and\; (RO)_4B^-$. The stereoselectivity of lithium triisopropoxyborohydride(LIPBH) in the reduction of representative cyclic ketones was examined and compared with that of the potassium derivative.

• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.579-583
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• 1992

Stereoselective synthesis of farnesol, (2E, 6E)-3,7,11-trimethyldodeca-2,6,10-tiren-1-ol(1), was carried out using 5-bromo-2-methylpent-2-ene(2) as a starting material. After conversion of 5-bromo-2-methylpent-2-ene(2) to the corresponding iodide compound, 5-(4-methylpent-3-enyl)-2,3-dihydrofuran(4) was obtained by alkylation of 5-lithio-2,3-dihydrofuran with 5-iodo-2-methylpent-2-ene. Ni(0)-catalyzed coupling reaction of the dihydrofuran 4 with MeMgI was proceeded to give (3E)-4,8-dimethylnona-3,7-dien-1-ol(5) in 72% yield. The resultant homoallylic alcohol 5 was converted to the (5E)-6,10-dimethylundeca-5,9-dien-2-one(8) in 4 steps. Compound 8 was condensed with dimethylmethoxycarbonylmethylphosponate in benzene follwed by $NaBH_4$ reduction in EtOH to yield (2E, 6E)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol(1). Ni(0)-catalyzed coupling reaction of MeMgI with dihydrofuran 4 was a key step in this synthesis of farnesol(1).

• Bulletin of the Korean Chemical Society
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• v.23 no.1
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• pp.86-92
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• 2002

A short synthesis of novel prostanoids, 12-epi-carbacyclins 3 and 24, has been accomplished using palladium chemistry as a key step. The silyl enol ether 10a prepared through organopalladium chemistry has been allowed to react with 1-octen-3-one in the presence of $Pd(OAc)_2$ to give compound 12 in a single step. The unusual chemo- and stereoselective reduction of the ${\alpha},{\beta}$-unsaturated ketone in 12 has been effected with (S)-BINALH. Subsequent desilylation and Wittig reaction have provided the Subsequent desilylation and Wittig reaction have provided the $PGI_2$ analogues 3 and 24.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.12 no.11
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• pp.4940-4950
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• 2011

cis-(3R,5R)-Atorvastatin Ca (1) used for hyperlipidemia have four stereomers. However, It is very difficult to prepare stereoselective stereomers. In this paper, the reduction of 3,5-diketo atorvastatin ester (3) was performed using $Me_4NHB(OAc)_3$ in acetic acid as a reductant and showed excellent stereoselectivity in the double reduction of 3,5-diketo atorvastatin ester (3). As a result, reduction of compound 3 by $Me_4NHB(OAc)_3$ was purely obtained with cis-(3R,5R)-atorvastatin ester (4) of 1.5% and trans-(3R,5S)-atorvastatin ester (5) of 98.5%. Also, cis-(3R,5R)-atorvastatin Ca (1) and trans-(3R,5S)-atorvastatin Ca (7) were used to determine efficacy in the treatment of liver damage and hyperlipidemia induced by a high-fat diet in rats and to study the performance of the January 2010 experient was conducted. As a result, total cholesterol (TC), high-density lipoprotein-cholesterol (HDL-c), low-density lipoprotein-cholesterol (LDL-c), and triglyceride (TG) levels of compound 1 and 7 groups were $93.0{\pm}0.5$, $43.5{\pm}0.8$, $40.4{\pm}1.4$, $45.6{\pm}0.9\;mg/d{\ell}$ and $110.0{\pm}0.7$, $33.3{\pm}0.6$, $65.8{\pm}1.9$, $54.8{\pm}1.2\;mg/d{\ell}$, respectively. Atherogenic index (AI) and cardiac risk factor (CRF) in compound 1 and 7 were $1.14{\pm}0.05$, $2.14{\pm}0.05$ and $2.31{\pm}0.06$, $3.31{\pm}0.06$, aspartate aminotransferase (AST) and alanine aminotransferase (ALT) were $51.9{\pm}4.6$, $16.0{\pm}2.1\;IU/{\ell}$ and $75.8{\pm}4.4$, $35.1{\pm}9.7\;IU/{\ell}$. Taken together, while compound 1 treat against high-fat diet-induced hyperlipidemia by attenuating hepatic lipid depots and reducing oxidative stress, compound 7 group had a low curative effect on hyperlipidemia induced by a high-fat diet in rats. These findings suggest that new method about synthesis of stereoselective stereomers and indicate that it may consider using in a clinical trial.

• Analytical Science and Technology
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• v.5 no.3
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• pp.239-247
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• 1992

The complexations and selectivities of the 10 species of mono- and dimethylsubstituted anilinium ions with 18-crown-6 in methanol are examined at dropping mercury electrode. The stability constants of these complexes varies drastically due to the steric hindrance by the positions and numbers of methyl groups. And the analyses of the isomeric mixtures of methylanilinium, which are impossible to detect due to the overlapped peaks in normal conditions, were also accomplished by the additions of 18-crown-6 as the supporting complexing agent using the selective complexations by the steric hindrance effects. As results in case of the difference of stability, ${\Delta}log\;K$ were about 0.7~1.3, it was possible to confirm the existence of two species qualitatively. Otherwise when ${\Delta}log\;K$ were large than 1.6, the quantitative determinations of each species could be accomplished sucessfully. From these results it is deduced that the selective recongnition of the positions and numbers of methyl groups as the steric hindrance in anililniums by 18-crown-6 cause the large variation of the magnitudes of negative shift of reduction waves for guest ions in mixtures.