• Journal of the Korean Chemical Society
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• v.21 no.3
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• pp.155-160
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• 1977

HMO correlation diagrams for some competing 1,2-and 1,4-cycloaddition reactions have been made to elucidate the reaction mechanism. The main conclusions obtained from this study are as follows. 1) The crossing between the highest occupied molecular orbital and the lowest unoccupied molecular orbital was not observed, which indicates that the reaction proceeds thermally, in agreement with the experimental results. 2) From the consideration of the energy barrier in the process of the energy transformation going from reactants to product, the two-step mechanism via a diradical intermediate is preferred over the concerted one. 3) The existance of diradical intermediates can account for the observed product distributions.

• YAKHAK HOEJI
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• v.44 no.4
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• pp.325-333
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• 2000

The 1,3-dipolar cycloaddition reaction of the quinoxaline 4-oxides 2 with 2-chloroacrylonitrile gave the 2,3-dihydro-1H-1,2-diazepino[3,4-b]quinoxalines 3, which were converted into the 2,3,4,6-tetrahydro-1H-1,2-diazepino[3,4-b]quinoxalines 5-7. The reaction of compounds 3 with selenium dioxide in acetic acid/water resulted in ring transformation to give the 1,4-dihydro-4-oxopyridazino[3,4-b]quinoxalines 8.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.372-372
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• 2010

We have investigated adsorption of selenophene on Si(100) at room temperature using high resolution photoemission spectroscopy (HRPES) and near edge X-ray absorption fine structure (NEXAFS) in the partial electron yield (PEY) mode. The Si 2p, C 1s, Se 3d spectra of selenophene on Si(100) show that selenophene is nondissociatively chemisorbed on Si(100)-$2{\times}1$ through [2+2] cycloaddition. NEXAFS has been conducted to characterize the adsorption geometry of selenophene on Si(100). Since the $\pi^*$ orbital of C=C bond show good angular dependence in carbon K-edge NEXAFS spectra, the angle $53{\pm}5^{\circ}$ determined from NEXAFS spectra. This majority structure is consistent with the [2+2] cycloaddition of selenophene to the dimer of the Si(100)-$2{\times}1$ surface.

• Archives of Pharmacal Research
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• v.13 no.2
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• pp.126-131
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• 1990

The novel N-phenyl-2-furohydrazonyl chloride 4A and its p-nitro analog 4B have been prepared and identified. The cycloaddition reactions of nitrilimines 5A and 5B, derived by base catalyzed dehydrochlorination of 4A and 4B respectively, to a variety of dipolarophiles were investigated. The results showed that 4A and 4B are usuful precursors for synthesis of differently substituted 3-(2-furyl)-2-pyrazoline derivatives and their pyrazoles and analogs.

• Bulletin of the Korean Chemical Society
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• v.17 no.10
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• pp.909-918
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• 1996

Syntheses of carbapenam skeletons were achieved from 1,3-propanediol through 1,3-dipolar cycloaddition. 3-(Tetrahydropyran-2-yloxy)-(10) and 3-(t-butyldimethylsilyloxy) propanal (13) were obtained from 1,3-propanediol. 3-Hydroxypropanals (10, 13, 14) were reacted with N-hydroxyglycine esters to give C-(2-hydroxyethyl)-N-alkoxycarbonylmethylnitrones (15a-15d). 1,3-Dipolar cycloaddition of the nitrones with methyl acrylate or ethyl crotonate gave 3-(2-hydroxyethyl)isoxazolidines (16a-16b, 17a-17b, 18, 19a-19b). 3-(2-Hydroxyethyl)isoxazolidines (17a, 17c, 19a, 19b) were converted to 3-(2-iodoethyl)isoxazolidines (21a-21d) or 3-phenylthiocarbonylmethylisoxazolidines (25a-25d) which were cyclized to give 2-oxa-1-azabicyclo[3.3.0]octanedicarboxylates (22a-22d, 26a-26d). 2-Oxa-1-azabicyclo[3.3.0]octane-4,8-dicarboxylates (22c-22d, 26c-26d) were transformed to 6-(l-hydroxyethyl)carbapenam-3-carboxylates (30a-30b, 31a-31b).

• Bulletin of the Korean Chemical Society
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• v.15 no.5
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• pp.337-338
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• 1994

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.136-136
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• 2013

High-resolution photoemission spectroscopy (HRPES) measurements were collected and density functional theory (DFT) calculations were conducted to track the coverage dependent variation of the absorption structure of 2-thiophenecarboxaldehyde (C4H3SCHO: TPCA) on the Ge(100) surface at room temperature. In an effort to identify the most probably adsorption structures on the Ge(100) surface, we deposited TPCA molecules at a low coverage and at a high coverage and compared the differences between the electronic features measured using HRPES. The HRPES data provided three possible adsorption structures of TPCA on the Ge(100) surfaces, and DFT calculations were used to determine the plausibility of the structures. HRPES analysis, corroborated by DFT calculations, indicated that an S-dative bonded structure was the most probable adsorption structure at relatively lower coverage levels, the [4+2] cycloaddition structure was the second most probable structure, and the [2+2]-C=O cycloaddition structure was the last probable structure on the Ge(100) surfaces at relatively higher coverage levels.

• Bulletin of the Korean Chemical Society
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• v.19 no.10
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• pp.1080-1083
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• 1998

An efficient method for construction of 2-arylfiirans has been developed by ceric(IV) ammonium nitratemediated oxidative cycloaddition of cyclic and acyclic 1,3-dicarbonyl compounds to several alkynes. Reactions of 1,3-cyclohexanedione, 1,3-cyclopentanedione, and 2,4-pentanedione with several alkynes furnish 2-arylfurans in 26-75% yields. Extension of this technology to more complex 4-hydroxy-2-quinolone and 3-hydroxy-lH-phenalen-l-one with phenylacetylene also affords furoquinolinone and ftirophenalenone derivative in moderate yields. Reaction of 4-hydroxycoumarins with phenylacetylene give linear and angular furocoumarin derivatives as a mixture of regioisomer in good yields. The mechanistic pathway for the formation of 2-arylfurans has been also described.

• Journal of the Korean Magnetic Resonance Society
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• v.27 no.2
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• pp.10-15
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• 2023

The Strain-Promoted Azide-Alkyne Cycloaddition (SPAAC) is a powerful method for synthesizing triazoles, even under physiological conditions, without a copper catalyst. This technique provides an efficient means for everyone to synthesize complex triazole derivatives rapidly. In order to investigate the configuration of triazole derivatives using bicyclo[6.1.0.]-nonyne (BCN) and chiral azide, it is necessary to employ the 2D NMR. Both 1D and 2D NMR (COSY, HSQC, ¹⁵N HMBC) are used to analyze the complex triazole product containing cyclooctyne, a diastereomeric product. The stereometric difference of the proton bonded to the same carbon is determined through the HSQC assignment. The intriguing splitting pattern of carbon resonances also reveals their diastereomeric configuration and will aid in further research based on physiological knowledge.

• Archives of Pharmacal Research
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• v.15 no.4
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• pp.292-297
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• 1992

Coupling of naphthacylpyridinium bromide 2 [1-(2-naphthyl) ethanone-2-pyridinium bromide] with N-nitrosoacetarylamides afforded C-(2-naphthoyl)-N-arylmethanohydrazonoylpyridinium bromides 3A-C. Treatment of 3A-C with base afforded the corresponding tetrazines 6A-C. Cycloaddition of nitrilimines 5A-C to N-arylmaleimides, acrylonitrile, ethyl acrylate, acrylamide, fumaronitrile, $\alpha$-cyanocinnamonitriles, ethyl $\alpha$-cyano-p-nitrocinnamates and $\alpha$-cyano-p-nitrocinnamamide afforded the corresponding cycloadducts 7-14, respectively. The cycloadducts 11-14 undergo a facile thermal elimination of hydrogen cyanide to give the corresponding pyrazoles 18-21 respectively.