• Bulletin of the Korean Chemical Society
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• 제19권9호
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• pp.957-961
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• 1998

Intramolecular Diels-Alder cycloadditions of 2-pyrone-3-carboxylates with trans-vinyl silaketal groups tethered via a chiral, non-racemic 1,3-butanediol auxiliary proceeded in unexpected stepwise cycloadditions through ionic intermediates to provide cis-disubstituted bicylolactones. The ratio of two isomers, exo and endo, was 5 to 1, and each isomer was found to be diastereomerically pure (>99% de). Their relative and absolute stereochemistries were determined by $^1H$ NMR spectroscopy and confirmed by X-ray crystallography of minor, endo-adduct 9. The major exo-adduct was successfully transformed to (-)-2-butyl substituted A-ring phophine oxide 16, a key element for the synthesis of 2-butyl vitamin D3.

• Bulletin of the Korean Chemical Society
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• 제17권5호
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• pp.428-432
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• 1996

Amino acid cobalt(Ⅲ) complexes of 1,3-diminopropane-N,N'-di-α-(β-methyl)-pentanoic acid (H2dpdmp), uns-cis-[Co(dpdmp)(aa)] (aa=glycine, S-alanine, R-aspartic acid, sarcosine) have been prepared from the reaction between the uns-cis-[Co(dpdmp)Cl2]- complex and the corresponding amino acid. In the reaction with the uns-cis-[Co(dpdmp)Cl2]- complex, glycine and S-alanine have yielded both merridional and facial isomers, while R-aspartic acid and sarcosine, only merridional isomers. The stereospecific substitution reaction of R-aspartic acid to racemic uns-cis-[Co(dpdmp)Cl2]- complex has yielded two merridional diastereomers; ΛR-uns-cis- and ΛR-uns-cis-[Co(dpdmp)(R-asp)]. It is of interest to note that this is one of the few CoⅢ(ONNO)(aa) type complex preparations, which gives only one isomer with stereospecificity. On the other hand, two merridional products obtained from the reaction of sarcosine with racemic uns-cis-[Co(dpdmp)Cl2]- are turned out to be mixtures of optical isomers.

• Bulletin of the Korean Chemical Society
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• 제20권4호
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• pp.436-440
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• 1999

The highly resolved absorption spectra of mer-[Cr(dpt)(Gly-Gly)]ClO4·H2O [dpt = di(3-aminopropyl)amine, H2Gly-Gly = glycylglycine] have been measured between 13000 cm-1 and 50000 cm-1 temperatures down to 2 K. The vibrational intervals were extracted by recording emission and far-infrared spectra. The characteristic infrared bands in meridional isomer were discussed. The four-teen electronic origins due to spin-allowed and spin-forbidden transitions were assigned. With the use of this electronic transitions, a ligand field optimization based on the exact known ligand geometry have been performed to determine more detailed bonding properties of Gly-Gly and dpt ligands. It is confirmed that the peptide nitrogen of the Gly-Gly has a weak π-donor property toward chrornium(Ⅲ) ion.

• Bulletin of the Korean Chemical Society
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• 제17권12호
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• pp.1112-1117
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• 1996

The electronic structures of twenty-seven isomers of a macrocyclic fulleropyrrolidine are investigated with semi-empirical extended Huckel (EH) molecular orbital method. The geometry of each isomer is determined by the molecular mechanics and dynamics methods based on UFF (universal force field) empirical force field. The calculated geometries, such as the carbon-carbon distances of the fullerene moiety, are in good agreement with those of related fullerene derivatives. The EH calculation shows that the formation of macrocyclic pyrrolidine ring on fullerene moiety results in the reduction of the HOMO-LUMO energy gap. From the graphical analysis of the DOS (density of states), PDOS (projected DOS), and MOOP (molecular orbital overlap population) curves, we can find that this reduction is due to splitting of the HOMO of fullerene moiety, which results from the symmetry-breaking and the distortion of the buckminsterfullerene framework from its ideal icosahedral structure.

• Bulletin of the Korean Chemical Society
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• 제17권12호
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• pp.1147-1149
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• 1996

The trans (2a)-cis (2b) isomerization of [Me2Al(μ-NHtBu)]2 (2) has been studied by 1H NMR spectroscopy. The equilibrium has been observed to follow reversible first order kinetics with ΔH0=2.22±0.07 kJmol-1 and ΔS0=2.85±0.07 JK-1mol-1. The activation parameters for the conversion 2a→2b are ΔH1=49.7±2.3 kJmol-1 and ΔS1=-126.3±0.2 JK-1mo1-1 and for the reverse reaction 2b→2a are ΔH-1=47.5±2.3 kJmol-1 and ΔS-1=-129.1±0.5 JK-1mol-1. The isomerization is markedly accelerated in the presence of Lewis bases. A crossover experiment indicates that the isomer interconversion is a unimolecular process. The large negative entropies of activation suggest either the existence of a sterically congested intermediate or the participation of solvent in the isomerization process.

• Bulletin of the Korean Chemical Society
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• 제19권5호
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• pp.533-539
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• 1998

A magnetic film was deposited on a slide glass substrate from aqueous solutions of $FeCl_2$ and $NaNO_2$ at 363 K. XRD analysis showed that the film was polycrystalline magnetite $(Fe_{3(1-{\sigma})}O_4)$ without impurity phase. The lattice constant was 0.8390 nm. Mossbauer spectrum of the film could be deconvoluted by the following parameters: isomer shifts for tetrahedral $(T_d)$ and octahedral $(O_h)$ sites are 0.28 and 0.68 mm/s, respectively, and corresponding magnetic hyperfine fields are 490 and 458 kOe, respectively. The estimated chemical formula of the film by the peak intensity of Mossbauer spectrum was $Fe_{2.95}O_4$. Low temperature transition of the magnetite (Verwey transition) was not detected in resistivity measurement of the film. Properties of the film were discussed with those of pressed pellet and single crystal of synthetic magnetites. On the surface of the film, magnetite particles of about 0.2 μm in diameter were identified by noncontact atomic force microscopy (NAFM) and magnetic force microscopy (MFM).

• 대한방사성의약품학회지
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• 제4권2호
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• pp.106-114
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• 2018

Angiogenesis is the new blood vessel formation process and has known to a fundamental event of tumor growth and metastasis. Especially, vascular endothelial growth factor (VEGF) and VEGF receptors (VEGFRs) are the crucial regulators of angiogenesis in tumor. VEGF-A is one of the VEGF family and binds to endothelial cell specific VEGFR1 and VEGFR2, which are associated with tumor growth and tumor angiogenesis. $VEGF_{121}$ is more tumorigenic isomer of VEGF-A. Targeted VEGF or VEGFR molecular imaging has been widely used to enable diagnosis and monitoring of proliferation and development of angiogenic tumors. Therefore, in this review, we have focused on the radioligands with $VEGF_{121}$ for angiogenesis of tumor.

• Bulletin of the Korean Chemical Society
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• 제5권5호
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• pp.191-193
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• 1984

6, 6-Diiodopenicillanic acid was prepared from 6-aminopenicillanic acid using iodine-sodium iodide systems in good yield (60%). Enolates derived from 6-chloro-6-iodo-, 6,6-diiodo-penicillanate have been generated in situ by a metal-halogen exchange process at -$78^{\circ}C$ using methylmangnesium iodide and reacted with acetaldehyde to yield aldols. As the size of remaining halogen atom increases, the proportion of ${\beta}$-face attack was increased. In the case of 6,6-diiodopenicillanate, only ${\beta}$-face attack was observed yielding a single isomer (6S, 8R).

• Bulletin of the Korean Chemical Society
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• 제7권3호
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• pp.201-204
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• 1986

Reduction of N-arylpyridinium compounds by $NaBH_4$ gave mixtures of the corresponding 1,2-dihydropyridine(major) and 1,4-dihydropyridine(minor), whereas similar reduction by $Na_2S_2O_4$ produced 1,4-dihydropyridines regioselectively. The proportion of 1,4-isomer in the product by $NaBH_4$ reduction appeared to increase with the electron-donating ability of N-aryl groups. When the N-aryl group is p-methylphenyl, p-ethylphenyl or p-methoxyphenyl, the 1,2-dihydropyridines in ethanol-water (4:1) solutions isomerized to the corresponding 1,4-dihydropyridines. N-(p-methylphenyl)-1,2-dihydropyridine and N-(p-ethylphenyl)-1,2-dihydropyridine in solid state also isomerized to the corresponding 1,4-dihydropyridines. The different behaviors of reduction among N-arylpyridiniums and isomerization of the reduction products depending on the substituent in N-aryl group were explained in terms of difference in the electronic effects of the substituents.

• Bulletin of the Korean Chemical Society
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• 제11권3호
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• pp.251-253
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• 1990

L-Alanine(L-ala) and S-methyl-L-cysteine(L-mcy) cobalt(III) complexes of a flexible $N_2O_2$-type tetradentate ligand ethylenediamine-N,N'-di- -butyric acid(eddb), s-cis-[Co(eddb)(L-ala)] and s-cis-[Co(eddb)(L-mcy), have been prepared via the substitution reactions of the s-cis-$[Co(eddb)Cl_2]$-complex with, respectively, L-alanine and S-methyl-L-cysteine. Both L-alanine and S-methyl-L-cysteine are found to coordinate to the cobalt(III) ion via the nitrogen and oxygen donor atoms to give the meridional s-cis isomer. Electronic absorption, ir and pmr spectra are used to characterize the complexes obtained in this work along with elemental analysis data.