• Bulletin of the Korean Chemical Society
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• v.26 no.9
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• pp.1359-1365
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• 2005

A series of new chiral [iminophosphoranyl]ferrocenes, {${\eta}^5-C_5H_4-(PPh_2=N-2,6-R_2-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-PPh^2-2-CH(Me)NMe_2$} (1: R = Me, $^iPr$), {${\eta}^5{-C_5H_4-(PPh_2=N-2,6-R_2}^1-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-(PPh_2=N-2,6-R_2-C_6H_3)-2-CH(Me)R_2$} (2: $R^1\;=\;Me,\;^iPr;\;R^2\;=\;NMe_2$, OMe), and $({\eta}^5-C_5H_5)Fe${${\eta}^5-C_5H_4-1-PR_2-2-CH(Me)N=PPh_3$} (3:R = Ph, $C_6H_{11}$) have been prepared from the reaction of [1,1'-diphenylphosphino-2-(N,N-dimethylamino) ethyl]ferrocene with arylazides (1 & 2) and the reaction of phosphine dichlorides ($R_3PCl_{2}$) with [1,1'-diphenylphosphino-2-aminoethyl]ferrocene (3), respectively. They form palladium complexes of the type $[Pd(C_3H_5)(L)]BF_4$ (4-6: L = 1-3), where the ligand (L) adopts an ${\eta}^2-N,N\;(2)\;or\;{\eta}^2$-P,N (3) as expected. In the case of 1, a potential terdentate, an ${\eta}^2$-P,N mode is realized with the exclusion of the –=NAr group from the coordination sphere. Complexes 4-6 were employed as catalysts for allylic alkylation of 1,3-diphenylallyl acetate leading to an almost stoichiometric product yield with modest enantiomeric excess (up to 74% ee). Rh(I)-complexes incorporating 1-3 were also prepared in situ for allylic alkylation of cinnamyl acetate as a probe for both regio- and enantioselectivities of the reaction. The reaction exhibited high regiocontrol in favor of a linear achiral isomer regardless of the ligand employed.

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1617-1621
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• 2012

The titanate nanotube (TNT) was hydrothermally synthesized in 10 M NaOH aqueous solution at $150^{\circ}C$ for 72 h. Titanate nanotube with high surface area (292 $m^2$/g) is a good candidate as a support for catalytic reaction or organic synthesis. Palladium nanoparticles with an average size of $ca$. 3 nm were well dispersed onto the surface of TNT nanotubes. Palladium loaded catalyst with high surface area shows a highly efficient ${\alpha}$ alkylation of ketones with primary alcohols.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.200-200
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• 2011

Hierarchical mesoporous ZSM-5 with enhanced mesoporosity was synthesized by microwave through the rapid assembly via ionic interaction between sulfonic acid functionalized ZSM-5 nano particles and cationic surfactant. The catalytic performance of enhanced accessibility due to mesoporosity and acidity were investigated in the alkylation of mesitylene with benzyl alcohol as alkylating agent. The effect of mole ratio of aromatic with benzyl alcohol, reaction time and alkylation agent were also studied. The enhanced mesoporosity and acidity of sulfonic acid functionalized mesoporous ZSM-5 induced activity enhancement compared with non-functionalized mesoporous ZSM-5, sulfonic functionalized mesoporous ZSM-5 synthesized by hydrothermal method and conventional microporous ZSM-5. The sulfonic acid functionalized mesoporous ZSM-5 showed much higher chemoselectivity of benzylated mesitylene than others, whereas the others mainly show dibenzyl ether as product. This significant difference in catalytic selectivity was resulted from the existence of mesopores, which definitely allowed the benzylation in mesopores.

• Bulletin of the Korean Chemical Society
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• v.23 no.5
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• pp.749-757
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• 2002

Chiral oxazolidin-2-one is easily prepared from D-mannitol and demonstrated to undergo highly diastereoselective alkylation reactions via lithium imide Z-enolates of its N-acyl derivatives to afford ${\alpha}-branched$ products. Evans syn and non-Evans sy n aldol products were also selectively obtained using this new auxiliary in high diastereomeric purity by simply changing the stoichiometry of TiCl4 and the nature of the amine base. Also, this new auxiliary is employed in diastereoselective Staudinger-type ${\beta}-lactam$ syntheses. Using 2-chloro-1-methylpyridinium iodide as the dehydrating agent, the reaction of auxiliary tethered acetic acid with trans imines gave the desired ${\beta}-lactams$ with cis-selectivity.

• Archives of Pharmacal Research
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• v.28 no.2
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• pp.129-141
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• 2005

(-)-Fumagillol (1), a hydrolysis product of fumagillin, has been synthesized by several group from commercially available 1,2:5,6-di-O-isopropylidene-${\alpha}$-D-allofuranose in a highly stereoselective manner. Chiral centers on C5 and C6 came from D-allofuranose and the asymmetric center on C4 was accomplished by 1,3-chirality transfer using the Claisen rearrangement on a chiral allyl alcohol. Chirality, which is necessary on an epoxide consisting of the spiro-ring system, was diastereoselectively constructed by the well-known reaction, intramolecular ester enolate alkylation (IEEA), which showed that this reaction can be applied to the alpha-alkoxy ester system. The epoxide on the side chain was regioselectively introduced by the difference between the number of substituents on the vinyl groups. This accomplishment proved that IEEA can be a useful tool for the synthesis of complex molecules.

• Archives of Pharmacal Research
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• v.19 no.2
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• pp.148-152
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• 1996

The efficient synthesis of 4-(2-thiazolyloxy)phenylalkanoic acids (10a-c), which are a potent antiinflammatory agent, was achieved in 5-6 steps starting from isopropoxybenzene and methyl $\alpha-chloro-\alpha-(methylthio)acetate (1)$. The key intermediate (4) was prepared by Friedel-Crafts reaction of isopropoxybenzene with (1) followed by desulfurization and the removal of isopropyl protector. Methyl 4-hydroxyphenylalkanoates (6, 8) were similarly obtained from alkylation of (3) and deprotection.

• Journal of the Korean Chemical Society
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• v.60 no.5
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• pp.374-377
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• 2016

• Journal of the Korean Chemical Society
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• v.43 no.1
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• pp.27-131
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• 1999

• Bulletin of the Korean Chemical Society
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• v.31 no.11
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• pp.3382-3384
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• 2010

A new synthetic route to ($\pm$)-aspidospermidine was devised, starting from the cycloadduct of 3-ethyl-5-bromo-2-pyrone with vinyl sulfide through a tandem conjugate addition-alkylation sequence. The requisite 3-ethyl-5-bromo-2-pyrone was prepared via the C3-selective Pd-catalyzed coupling reaction with $Et_3Al$-dimethylaminoethanol complex.

• Applied Chemistry for Engineering
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• v.8 no.2
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• pp.211-219
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• 1997

Liquid or gas phase alkylation of isobutane with 1-butene for i-octane production was carried out over Cs- or $NH_4$-exchanged $H_3PW_{12}O_{40}$. Pretreatment temperature of the catalyst played an important role on the catalytic activity of heteropoly acids in the liquid phase alkylation. Cation-exchanged $H_3PW_{12}O_{40}$ showed a better total yield and i-octane selectivity than the mother acid in the liquid phase alkylation, and $(NH_4)_{2.5}H_{0.5}PW_{12}O_{40}$ was more efficient than $Cs_{2.5}H_{0.5}PW_{12}O_{40}$ in terms of i-octane selectivity. It was found that the acidic property (deactivation of acid sites) of the catalyst was closely related to the catalytic activity of Cs- or $NH_4$-exchanged $H_3PW_{12}O_{40}$ in the gas phase alkylation. $C_5-C_7$ were mainly formed in the early stage of gas phase alkylation due to the strong acidic property of the catalyst, whereas $C_8$ and $+C_9$ were mainly produced as the reaction proceeded due to the deactivation of acid sites. $Cs_{2.5}H_{0.5}PW_{12}O_{40}$ showed the highest total yield in the gas phase alkylation among the catalysts examined.