• Bulletin of the Korean Chemical Society
• /
• v.4 no.5
• /
• pp.197-200
• /
• 1983

The Diels-Alder cycloaddition reactions between dienes and allenic ketones were studied theoretically using CNDO/2 method. It was found that the reaction is a neutral electron demand type with matrix element control and the reactivity, the regio- and stereo-selectivities can be correctly predicted based on interaction energies calculated with the 4-center FMO formalism.

• Bulletin of the Korean Chemical Society
• /
• v.7 no.3
• /
• pp.210-213
• /
• 1986

1,1-Dicyano-2-ethoxycyclobutane (1a) was prepared by [2 + 2] cycloaddition reaction of vinylidene cyanide with ethyl vinyl ether. 1,1-Dicyano-2-phenylcyclobutane (1b) was prepared by the reactions involving the reduction of cinnamyl alcohol, chlorination, cyanomethylation, bromination, and ring-closure reaction. Compound 1a was ring-opening polymerized with NaCN or n-butyllithium to give a low molecular weight polymer. The compound 1b however, failed to polymerize by either anionic or radical catalysts.

• Bulletin of the Korean Chemical Society
• /
• v.10 no.3
• /
• pp.289-292
• /
• 1989

Electronic structures and ethylene addition reaction for halocyclopentynes are investigated using MNDO method. Electronic effects due to the halogen substitution are very small for halocyclopentynes. Fluorocyclopentyne is slightly more stable than cyclopentyne and other halocyclopentynes, but reactivities for cycloaddition reactions are about the same for all halocyclopentynes and cyclopentyne. Stabilization effect is substantial for hexafluorocyclopentyne.

• Bulletin of the Korean Chemical Society
• /
• v.17 no.4
• /
• pp.314-321
• /
• 1996

Isoxazolidine derivatives 7 and 8 were synthesized from N-benzyl-C-(2-benzyloxyethyl)nitrones by 1,3-dipolar cycloaddition with ethyl crotonate. The isoxazolidine derivatives were converted to β-amino acid esters 9a and 9b by reduction with zinc in acetic acid. The β-amino acid esters were reacted with methylmagnesium bromide to give the 2-azetidinones (13a, 13b). The benzyl group of 2-azetidinones were removed by Birch reduction. The products were oxidized with PDC to give 3-[1-(t-butyldimethylsilyloxy)ethyl]-4-carboxymethyl-2-azetidinone derivatives (2a, 2c).

• Proceedings of the PSK Conference
• /
• 2003.04a
• /
• pp.240.2-240.2
• /
• 2003

A strategy for synthesis of the furan-fused tetracyclic core of xestoquinone and halenaquinone was explored through a model study. Methyl 8-oxo-4-methyl-4-phenyl-2,7-nonadiynoate was prepared from hydratroponitrile and 3-butyn-1-ol as starting materials. The intramolecular cycloaddition of this intermediate as a key step will be involved.

• Proceedings of the PSK Conference
• /
• 2003.10b
• /
• pp.65.1-65.1
• /
• 2003

Natural benzo[c]phenanthridine and protoberberine alkaloids which have been attractive to synthetic organic chemists and biochemists over the last 2 decades since such compounds have shown interesting biological properties such as antitumor, antiviral and antimicrobacterial activities. For the systematic research on these alkaloids, several total syntheses of these alkaloids have been reported. However, the bulk of reported benzo[c]phenanthridine synthetic studies to date have involved multistep sequences for assembly of the target molecules as well as lack of generality for synthesizing substituted molecules. (omitted)

• Korean Chemical Engineering Research
• /
• v.48 no.5
• /
• pp.621-626
• /
• 2010

In this study, imidazole-based ionic liquid on polystyrene was prepared and its catalytic performance in the cycloaddition of $CO_2$ with allyl glycidyl ether(AGE) to produce allyl glycidyl carbonate was investigated. The ionic liquid was generated on the polystyrene-based polymer through the immobilization of imidazole. The prepared catalyst was characterized using a number of instrumental analysis including EA, FT-IR, TGA and SEM. The immobilized ionic liquid showed very good catalytic activity for the cycloaddition of $CO_2$ with AGE, having 80% of AGE conversion with over 96% of the carbonate selectivity at $120^{\circ}C$ under 1.48 MPa $CO_2$ pressure. The immobilized ionic liquid can be used for the reaction up to four consecutive runs without significant loss of its catalytic activity.

• Journal of the Korean Chemical Society
• /
• v.31 no.2
• /
• pp.133-142
• /
• 1987

Stereoselectivities of (4+2) cycloaddition reactions of cyclopentadiene with the methyl-substituted allenic acids and esters were investigated by application of $\pi$-nonbonded interaction ($\pi$-NBI) theory. 2-FMO method has been found to be adequate for determination of endo selectivities of diene(LUMO)-dienophile (LUMO) interaction in the thermal reactions and diene (HOMO)-dienophile (LUMO) interaction in the Lewis acid catalyzed reactions. $\pi$-isoconjugate diene structure was formed by through-bond interaction of allene moiety with methyl group in the cumulated diene system; the methyl substituent acts as a conjugative chain and causes inter-level narrowing effect of the FMO's. In dienophiles which do not form $\pi$-isoconjugate diene system, methyl group acts merely as an electron donating group. In thermal reactions, the stereoselectivities are controlled by $\pi$-nonbonded secondary orbital interaction ($\pi$-NSOI) of methyl substituent, which behaves similarly as an ethylene molecule.

• Applied Chemistry for Engineering
• /
• v.31 no.3
• /
• pp.258-266
• /
• 2020

The chemical fixation of CO₂ into cyclic carbonates is considered to be one of the most promising way to alleviate global warming and produce fine chemicals. In this work, the catalytic applicability of metal-organic frameworks (MOFs) as porous crystalline materials for the synthesis of five-membered cyclic carbonate from CO₂ and epoxides was reviewed. In addition, we have briefly classified the materials based on their different structural features and compositions. The studies revealed that MOFs exhibited good catalytic performance towards cyclic carbonate synthesis because of the synergistic effect between the acid sites of MOFs and nucleophile. Moreover, the effect of structure of designed MOFs and mechanism for the cycloaddition of CO₂ were suggested.

• Applied Chemistry for Engineering
• /
• v.27 no.2
• /
• pp.153-157
• /
• 2016

In this study, three different metal-containing ionic liquid catalysts were prepared by metal insertion and characterized by various physicochemical analytic methods. The catalytic performance of the metal containing ionic liquids in the cycloaddition of $CO_2$ with propylene oxide (PO) to produce propylene carbonate (PC) was investigated under the solvent free condition. The order of approximate rate constants ($K_{app}$) for the metal containing ionic liquid catalysts was $(MeIm)_2ZnCl_2$, > $(MeIm)_2FeCl_2$ > $(MeIm)_2CuCl_2$. These results are in accord with the experimentally obtained activity order of the different metal containing ionic liquid catalysts.