• Title/Summary/Keyword: cycloaddition

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Density Functional Study on [3+2]-Dipolar Cycloaddition Reaction of the N-heterocyclic Carbene Boryl Azide with Olefins

  • Zhang, Xing-Hui;Wang, Ke-Tai;Niu, Teng;Li, Shan-Shan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.5
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    • pp.1403-1408
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    • 2014
  • The cycloaddition reactions of the N-heterocyclic carbene boryl azide with methyl acrylate, butenone, and hexafluoropropene have been investigated theoretically. Solvent effects on these reactions have been explored by calculation that included a polarizable continuum model (PCM) for the solvent (C6H6). The title reaction could produce 4- and 5-substituted 1,2,3-triazolines, respectively. The reaction systems have the higher chemical reactivity with the low barriers and could be favored. Yet the smaller differences have been found to occur in energetics, and the cycloaddition reactions occur for s-trans conformations over s-cis conformations. The calculations indicated that the cycloaddition reaction of the alkenes have certain regioselectivity.

Control over [2+2+2] and Carbonylative [4+2] Cycloaddition by CO Pressure in Co-Catalyzed Cycloaddition between Internal Diynes and Cyclopentadiene

  • Kim, Do-Han;Chung, Young-Keun;Han, Jin-Wook
    • Bulletin of the Korean Chemical Society
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    • v.29 no.6
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    • pp.1224-1228
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    • 2008
  • The reaction of internal diynes and cyclopentadiene in the presence of 5 mol % of cobalt catalysts proceeded under 5 atm of carbon monoxide pressure to give a high yield of the corresponding [2+2+2] cycloaddition product. By lowering carbon monoxide pressure from 30 atm to 5atm, cyclopentadiene can be used as a dienophile in the cobalt carbonyl-catalyzed [2+2+2] cycloaddition reaction between internal diynes and cyclopentadiene.

Effect of Themperature on the 1,3-dipolar Cycloaddition of 3-phenyloxadiazole Derivatives (3-Phenyloxadiazole 유도체의 1,3-dipolar Cycloaddition 반응에 미치는 온도의 영향)

  • Hwang, Sung-Kwy;Lee, Ki-Chang;Choi, Bong-Jong;Lee, Kwang-Ill
    • Journal of the Korean Applied Science and Technology
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    • v.14 no.3
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    • pp.39-46
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    • 1997
  • Ultraviolet spectrophotometric investigation has been carried out on the rate constants for 1,3-dipolar cycloaddition of 4-substituted-3-phenyloxadiazole derivatives with dipolarophiles such as phenyl acetylene, propiolic acid methyl ester and dimethylacetylene dicarboxylate. From there, the rate constants for 1,3-dipolar cycloaddition were determined at 80, 100 and $120^{\circ}C$, and the reaction rates were increased with increasing temperature. From these rate constants, the values of the thermodynamic activation parameters were obtained. Some thermodynamic activation parameters such as $E_{\alpha}$, ${\Delta}H^{\ast}$, ${\Delta}S^{\ast}$ and ${\Delta}G^{\ast}$ from Arrhenius equation were also calculated for the electrophilic 1,3-dipolar cycloaddition of 3-phenyloxadiazole derivatives with dipolarophiles. In order to the proposal the mechanism and reactivity of 1,3-dipolar cycloaddition reaction, the effect of substituents having various kinds of electron withdrawing or releasing groups were examinated. Considering the effect of substituents, an electron withdrawing group attached at the 4-carbon position in 3-phenyloxadiazole derivatives decreases the reaction rate because of the lack of electron density in 3-phenyloxadiazole ring.

Application of Silica-supported Ionic Liquid Catalysts to Cycloaddition of CO2 (CO2 부가반응에 적용된 Silica 담지 이온성 액체 촉매)

  • Kim, Dong-Woo;Kim, Hyeon-Gook;Cho, Deug-Hee
    • Applied Chemistry for Engineering
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    • v.27 no.3
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    • pp.239-244
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    • 2016
  • The catalytic applicability of various ionic liquids immobilized on different silica-supports such as amorphous, SBA, MCM and commercial silica for the cycloaddition of $CO_2$ and epoxides is reviewed in this work. The effects of different structures of supported ionic liquids and silica supports in the synthesis cyclic carbonate by the cycloaddition of $CO_2$ have been remarked. The studies revealed that ionic liquids possessing functional groups or metals exhibited increased catalytic performance towards cyclic carbonate synthesis. Moreover, the reusability of SSIL catalyst and mechanism for the cycloaddition of $CO_2$ were studied.

Synthesis of Pyrazole derivatives via cycloaddition of 3-phenyloxadiazole derivatives with dipolarophiles (Oxadiazole유도체의 고리화 첨가반응에 의한 Pyrazole유도체의 합성)

  • Lee, Ki-Chang;Hwang, Sung-Kwy;Lee, Kwang-Ill;Choi, Bong-Jong
    • Journal of the Korean Applied Science and Technology
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    • v.14 no.1
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    • pp.95-102
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    • 1997
  • The synthetic method of pyrazole was performed by 1,3-dipolar cycloaddition with dipolarophile instead of the reaction between diazomethane and acetylene. The cycloaddition mechanism and reactivity of 3-phenyloxadiazole derivatives with dipolarophiles was investigated. In order to investigate the mechanism and reactivity of this cycloaddition, the effect of substituents having various kinds of electron withdrawing or releasing groups were examinated. Considering the effect of substituents, an electron withdrawing group attached at the 4-carbon position in 3-phenyloxadiazole derivatives decrease the reaction rate because of the lack of electron density in oxadiazole ring. The reaction rate of 3-phenyloxadiazole derivatives with dipolarophiles were more conveniently measured using UV than using a volumetric analysis which was used before. From the result of this study, it was that the cycloaddition was found to be a first-order reaction depending upon the concentration of 3-phenyloxadiazole only.

Synthesis of The Optically Active Bicyclo [4.2.0. ] octanone by Stereoselective Intramolecular [2+2] Cycloaddition (입체선택적인 분자내 [2+2] 환화반응을 이용한 광학활성 Bicyclo[4.2.0.]octanone의 합성)

  • Shim, Pil-Jong;Kim, Hee-Doo
    • YAKHAK HOEJI
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    • v.41 no.6
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    • pp.714-717
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    • 1997
  • Stereoselective synthesis of the optically active bicyclo [4.2.0] octanone 5 was accomplished using intramolecular olefin-keteniminium salt[2+2]cycloaddition of the amide 4 as a key step. This important chiral synthon was prepared starting from readily available L-glutamic acid via an efficient 8-step sequence.

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