• 제목/요약/키워드: diels-alder reaction

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시클로 펜타디엔과 구조적으로 회전이 쉬운 Dienophile간의 Diels-Alder 반응에 대한 이론적 연구 (Theoretical Studies on the Diels-Alder Reactions between Cyclopentadiene and Conformationally Flexible Dienophiles)

  • 김찬경;이인영;이본수;이익춘;김관수;주영협
    • 대한화학회지
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    • 제40권7호
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    • pp.483-491
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    • 1996
  • Cyclopentadiene과 exo-cyclic 이중결합을 가진 5각고리 화합물간의 Diels-Alder반응을 PM3 방법을 이용하여 연구하였다. Dienophile의 종류가 바뀌어도 전이상태의 구조는 커다란 변화를 나타내지 않았다. 반면에 dienophile의 exocyclic C(=O)-R 결합의 회w전에 의하여 나타나는 두 conformer들은 서로 다른 생성물을 얻을 수 있었으며, 이들의 반응성을 FMO들의 energy gap을 이용하여 설명하였다. 반면에 dienophile의 접근방향에 따른 exo, endo경로의 선택성을 살펴보기 위하여 전이상태에서의 deformation enerhy와 활성와 에너지간의 상관관계를 살펴보았다. 반응의 최저 에너지 경로를 Curtin-Hammett principle을 사용하여 논의 하였다.

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Synthesis and In vitro Evaluation of 4-Substituted-1-azaanthraquinones

  • Lee, Hee-Soon;Hong, Seoung-Soo;Choi, Jae-Young;Cho, Jung-Sook;Kim, Young-Ho
    • Archives of Pharmacal Research
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    • 제21권1호
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    • pp.73-75
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    • 1998
  • In summary, six 4-substituted-1-azzanthraquinones were designed and synthesized using hetero Diels-Alder reaction as a key step. Although a great number of reaction conditions for benzylic bromination were examined, this step need to be improved for the efficient synthesis of the related analogues. 4-Bromomethyl-1-azzanthraquinone 6 may have potential for the treatment of tumors resistant to the doxorubicin. The compounds 9 and 10 containing the latent alkylating functionality may need further in depth biological evaluation. Work is in progress to design, synthesize, and evaluate additional compounds in this and related systems.

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Elucidation of Selectivity Difference in the Diels-Alder Reactions of 6,6-Disubstituted Cyclohexa-2,4-dienone

  • Jeong, Jun-Pyeong;Lee, Oh-Seuk;Yang, Ki-Yull
    • Bulletin of the Korean Chemical Society
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    • 제23권6호
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    • pp.829-837
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    • 2002
  • Recently it was reported that cycloaddition of 6,6-disubstituted cyclohexa-2,4-dienone, 1 with cyclopentadiene gave solely the adduct of type 1.while its reaction with 1,3-cyclohexadiene gave both Ⅱ and Ⅲ. Semiempirical MO calculations were done to elucidate the origin of the selectivity difference between the two dienes. Cycloaddition of 1 with cyclopentadiene is controlled thermodynamically to give only 1-diene adduct by ΔGvalues of 10.6-20.3 kcal/mol, while its reaction with 1,3-cyclohexadiene does not show 1-diene/1-dienophile selectivity due to similar stabilities of the two adducts. Thermodynamic parameters also show that 두애 adducts are more fabourably fromed in the cycloadditions of 1 with both cyclopentadiene and 1,3-cyclohexadiene, which coincides with experimental observations. Cope rearrangements of endo adducts are another avenue to convert between 1-diene and 1-dienophile.

Photochemical C$_4$-Cycloadduct Formation between 5(E)-Styryl-1,3-dimethyluracil and Some Olefins-Via Photochemical Diels-Alder Type [4 + 2] Adduct

  • Shim, Sang-Chul;Shin, Eun-Ju
    • Bulletin of the Korean Chemical Society
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    • 제8권5호
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    • pp.376-380
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    • 1987
  • The cyclobutane forming photocycloaddition reaction of 5(E)-styryl-1,3-dimethyluracil with some olefins occurs on the 5,6-double bond of uracil ring rather than the expected central double bond via an intermediate, probably the photochemical Diels-Alder type adduct. This intermediate formed on short term irradiation of 5(E)-styryl-1,3-dimethyluracil and 2,3-dimethyl-2-butene solution is converted into the $C_4$-cycloadduct on the prolonged irradiation. Quantum yield of the intermediate formation is not linear with the concentration of 2,3-dimethyl-2-butene probably due to the secondary reaction accompanied with the complex reaction kinetics. The intermediate is formed from the lowest excited singlet state.

Synthesis of new Thebaine Derivatives with Phenylsulfonylpropadiene

  • Kim, Keun-Jae;Lee, Jung-Sei
    • Bulletin of the Korean Chemical Society
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    • 제10권2호
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    • pp.129-132
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    • 1989
  • Reactions of thebaine with phenylsulfonylpropadiene in various solvents were investigated. It was found that Diels-Alder reaction adduct was obtained in nonpolar solvent, while addition reaction adduct was obtained in polar solvent. Transformations of these two products were also carried out.

Diels-Alder Cycloaddition of Cyclopentadiene with Ethylacrylate Catalyzed by Mesoporous Al-MCM-48 and Al-MCM-41 Catalysts

  • Shon, Jeong-Kuk;Sim, Jae-Yi;Thakur, Santosh Singh;Ko, Eun-Mi;Kong, Soo-Sung;Choi, Ji-Yun;Kang, Min;Senapati, Bidyut Kumar;Choi, Doo-Seoung;Ryu, Do-Hyun;Kim, Ji-Man
    • Bulletin of the Korean Chemical Society
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    • 제29권10호
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    • pp.1993-1997
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    • 2008
  • In the present work, Diels-Alder reaction of cyclopentadiene with ethylacrylate has been carried out by using two types of mesoporous solid acid catalysts (Al-MCM-41, Al-MCM-48) with different pore structures. The specific topology of Al-MCM-48 (cubic Ia3d structure composed of two independent 3-D channel systems) exhibit higher activity and stereo-control than those of Al-MCM-41 (hexagonal packing of 1-D channels). The physical properties of Al-MCM-48 catalyst, such as high accessibility of reactants to the acid sites, spatial confinement in the nanoscopic reactors, and 3-D channel network structure that are effective adsorption and diffusion of reactants, play a crucial role in the present study.