• Bulletin of the Korean Chemical Society
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• v.32 no.5
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• pp.1662-1668
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• 2011

Steric and electronic parameters of 4'-substituents play significant roles in steering the conformation of nucleoside analogues. In order to investigate the relationship of 4'-substituent with antiviral enhancement, novel 4'-phenyl-5'-norcarbocyclic adenosine phosphonic acid analogues were racemically synthesized via de novo acyclic stereoselective route from propionaldehyde 5. The phenyl substituted cyclopentenols 15a and 15b as key intermediates were successfully constructed via reiterative carbonyl addition of Grignard reagents and ring-closing metathesis of corresponding divinyl 14. The synthesized nucleoside phosphonic acids analogues 19, 20, 21, and 23 were subjected to antiviral screening against HIV-1.

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.3880-3886
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• 2011

The nucleophilic substitution reactions of diisopropyl thiophophinic chloride (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $65.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.80-0.96). The anilinolyses of ten P=S systems in MeCN are reviewed on the basis of DKIEs and selectivity parameters to obtain systematic information on the DKIEs and mechanism for thiophosphoryl transfer reactions. The steric effects of the two ligands on reactivity, DKIEs, mechanism, and substituent effects of the nucleophile (X) on the DKIEs are discussed.

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2707-2710
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• 2012

The nucleophilic substitution reactions of O-ethyl phenyl phosphonochloridothioate with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are kinetically investigated in acetonitrile at $55.0^{\circ}C$. The deuterium kinetic isotope effects (DKIEs) invariably increase from a secondary inverse DKIE ($k_H/k_D$ = 0.93) to a primary normal DKIE ($k_H/k_D$ = 1.28) as the substituent of nucleophile (X) changes from electron-donating to electron-withdrawing. These can be rationalized by the gradual transition state (TS) variation from a backside to frontside attack. A concerted $S_N2$ mechanism is proposed. A trigonal bipyramidal TS is proposed for a backside attack while a hydrogen-bonded, four-center-type TS is proposed for a frontside attack.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.1042-1046
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• 2012

The kinetics and mechanism of the pyridinolysis ($XC_5H_4N$) of diethyl isothiocyanophosphate are investigated in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit the two discrete slopes with a break region between X = 3-Ac and 4-Ac. These are interpreted to indicate a mechanistic change at the break region from a concerted to a stepwise mechanism with rate-limiting expulsion of the isothiocyanate leaving group from a trigonal bipyramidal pentacoordinated intermediate. The relatively large ${\beta}_x$ values with more basic and less basic pyridines imply much greater fraction of frontside nucleophilic attack TSf than that of backside attack TSb.

• Bulletin of the Korean Chemical Society
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• v.33 no.10
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• pp.3203-3207
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• 2012

The nucleophilic substitution reactions of diisopropyl chlorothiophosphate (5) with X-pyridines have been kinetically studied in MeCN at $35.0^{\circ}C$. The Hammett and Br$\ddot{o}$nsted plots for the substituent X variations in the nucleophiles show biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 5 exhibits great negative deviation from the Taft plot. A concerted $S_N2$ mechanism is proposed involving a change of the attacking direction of the X-pyridines from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines.

• Bulletin of the Korean Chemical Society
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• v.35 no.5
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• pp.1329-1332
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• 2014

The kinetic studies on the reactions of O,O-diethyl Z-S-aryl phosphorothioates with X-pyridines have been carried out in dimethyl sulfoxide. The free energy correlations with X in the nucleophiles are biphasic concave upwards with a break point at X = H, while those for substituent Z variations in the leaving groups are linear. The negative sign of ${\rho}_{XZ}$ implies that the reaction proceeds through a concerted mechanism for both the strongly and weakly basic pyridines. The biphasic concave upward free energy relationships with X are rationalized by a change in the nucleophilic attacking direction from frontside with the strongly basic pyridines to backside with the weakly basic pyridines.

• Bulletin of the Korean Chemical Society
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• v.35 no.5
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• pp.1433-1439
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• 2014

We report on the influence of water as an electrolyte on the photovoltaic performances. The photovoltaic performance was shown to be quite sensitive to the substituent on the donor group. An optimized efficiency of 4.41% in the presence of 100% water content using $I^-/I{_3}^-$ redox couple was obtained using the D21L6 organic dye.

• Bulletin of the Korean Chemical Society
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• v.29 no.8
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• pp.1472-1478
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• 2008

The synthesis of a new series of 1$\beta$-methylcarbapenems having spiro[2,4]heptane moieties is described. Their in vitro antibacterial activities against both Gram-positive and Gram-negative bacteria were tested and the effect of substituents at the pyrrolidine ring was investigated. Most of the compounds were found to be more active compared to imipenem against Gram-negative bacteria. A particular compound (IIIc) having 7-oxo-5- azaspiro[2,4]heptane moiety showed the most potent antibacterial activity.

• Journal of the Korean Chemical Society
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• v.63 no.6
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• pp.435-439
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• 2019

An efficient one pot multicomponent synthesis of pyrimidinone derivatives of Biginelli type is described. 4-amino-6-aryl-pyrimidine-5-carbonitrile molecules were synthesized efficiently via three-component Biginelli-type condensation of aldehyde, malononitrile, and semicarbazone as urea substituent in the presence of a catalytic amount of PEG-400 as green medium under microwave irradiation. The reactions proceeded efficiently in the presence of microwave radiation to afford the desired products in good to excellent yields. Products have been confirmed by IR, and NMR spectral analysis. All the molecules were tested for their antimicrobial activity against E. coli, S. aureus, P. aeruginosa and C. tropicalis. Some of the compounds have shown moderate to good inhibition efficiency against both gram-positive and gram-negative bacteria. The potent activity was observed against the fungal species with minimum inhibition concentration 12.5 ㎍/mL.

• Journal of the Korean Chemical Society
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• v.29 no.5
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• pp.478-481
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• 1985

Nucleophilic substitution reactions between Alkanesulfonylchlorides and p-substituted anilines in methanol-acetonitrile mixture have been studied kinetically. Reactivities of substrates, substituent effects of nucleophile and solvent effects indicate that the studied reaction proceeds via $S_N2$. The kinetic results show that transition state of the reaction between i-PSC and anilines becomes looser as the composition of methanol increases.