• Title/Summary/Keyword: Intramolecular photocycloaddition

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Intramolecular [2+2] Photocycloaddition and Cycloreversion of Ferulic Acid Derivatives

  • Maeda, Hajime;Nishimura, Keisuke;Yokoyama, Akihiro;Sugimoto, Akira;Mizuno, Kazuhiko;Hosoda, Asao;Nomura, Eisaku;Taniguchi, Hisaji
    • Rapid Communication in Photoscience
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    • v.4 no.1
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    • pp.12-15
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    • 2015
  • Intramolecular photocycloaddition of ferulic acid derivatives proceeded in high yields to give head-to-head intramolecular photodimers as three atropisomers. The photocycloaddition was sensitized by triplet sensitizers such as benzophenone, whereas photocycloreversion was promoted by 9,10-dicyanoanthracene (DCA) as an electron-transfer photocatalyst. On the other hand, intermolecular photocycloaddition afforded a head-to-tail photodimer.

The Link Between Stereoselectivity and Spin Selectivity in Intermolecular and Intramolecular Photochemical Reactions

  • Griesbeck, Axel G.
    • Journal of Photoscience
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    • v.10 no.1
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    • pp.49-60
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    • 2003
  • How stereo selectivity in singlet and triplet photocycloaddition and photocyclization reactions, respectively, is linked to spin selectivity and how this link affects our understanding of photochemical reaction mechanisms, is described in this review. As illustrative examples, the Paterno-Buchi reaction and the Norrish-Yang cyclization are described with emphasis on triplet biradical structure and dynamics.

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Intramolecular Photocycloaddition of 3-(3-Butenyl)cycloher-2-enone and 3-(2-Propenoxy)cyclohex-2-enone in Zeolites

  • 노태희;권혁순;최경성;최경인
    • Bulletin of the Korean Chemical Society
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    • v.20 no.1
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    • pp.76-80
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    • 1999
  • The effects of zeolites on the intramolecular [2+2] photocycloadditions of 3-(3-butenyl)cyclohex-2-enone (la) and 3-(2-propenoxy)cyclohex-2-enone (lb) were investigated. When la adsorbed in cation-exchanged zeolites X and Y was irradiated through a Pyrex filter, the products from the 1,6-ring closure biradical increased compared to the results from the photoreaction in homogeneous solutions. In the intramolecular 1,5-ring closure photocycloaddition of la and lb, the products from the cis-fused intermediates increased in zeolites X and Y. The regiochemical and stereochemical outcomes of the photocycloadditions in the zeolites were interpreted by the binding of the guest molecules with the cations in the supercages.

The Effects of Media on the Intramolecular Photocycloaddition of 3-(3-Butenyl)cyclohex-2-enone

  • 노태희;최균선;박종욱
    • Bulletin of the Korean Chemical Society
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    • v.19 no.5
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    • pp.501-503
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    • 1998
  • In this work, we applied the 1D $11^B$ nutation NMR method for the analysis of the local structural environments in powdered borosilicates $(SiO_2-B_2O_3)$. Spin dynamics during a rf irradiation for spin I=3/2 was analytically calculated with a density ma trix formalism. Spectral simulation programs were written in MATLAB on a PC. Two borosilicates prepared by the sol-gel process at different stabilization temperature were used for the 1D $11^B$ nutation NMR experiment. The $11^B$ NMR parameters, quadrupole coupling constants $(e^2qQ/h)$ and asymmetry parameters (η), for each borosilicate were extracted from the nonlinear least-squares fitting. The effects of heat treatments on the local structures of boron sites in borosilicates were discussed.

Synthesis and Crystal Structure of 1,3-Diazatricyclo[5.3.1.$0^{5,11}$] undecane-2,4-dione (1,3-Diazatricyclo[5.3.1.$0^{5,11}$ undecane-2,4-dione의 합성과 결정구조)

  • 김정욱;윤호섭
    • Korean Journal of Crystallography
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    • v.5 no.2
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    • pp.100-107
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    • 1994
  • A new Nl-pentenyl derivative of pyrimidines has been synthesized by an intramolecular (2+2) photocycloaddition and characterized by the single-crystal X-ray diffraction technique. The compound crystallizes in the rhombohedral system (R3, a=27.767(5)A c=6.390(2)A). In this structure, two 6-membered rings and a 4-membered ring are fused by the N-N or N-C bonds and the Tyidin Part adouts chair conformation. A pair of molecules related by an inversion center we held together through the hydrogen bonding interactions between N and O atoms of the uracil miety.

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Formation and Cycloreversion of 2-Silacyclobuta[2.3]cyclophances via Photoinduced Electron Transfer

  • Mizuno, Kazuhiko;Nakanishi, Kazuhisa;Otsuji, Yoshio;Hayamizu, Tomoo;Maeda, Hajime;Adachi, Tomohiro;Ishida, Akito;Takamuku, Setsuo
    • Journal of Photoscience
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    • v.10 no.1
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    • pp.121-126
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    • 2003
  • Irradiation of an acetonitrile solution containing dimethylbis(4-vinylphenylmethyl)silane 1a in the presence of 9,10-dicyanoanthracene leads to formation of the intramolecular photocycloadduct, 2-sila-cyclobuta[2.3]cyclophane(2a). In contrast, prolonged irradiation gave insoluble polymeric material. The photocycloreversion of 2a occurs efficiently (quantum yields exceeds unity) by use of redox-type photosensitization in the presence of magnesium perchlorate. The transient absorption spectra generated by pulse radiolysis and gamma-radiolysis show that the radical cation species generated from 1a is different from that arising from 2a.

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X-Ray Crystal Structure Determination of Diazatricyclodione (디아자트리사이클로디온의 X선 결정구조 결정)

  • Kim, Sang-Su;An, Jong-Il;Han, Bo-Seop
    • Korean Journal of Crystallography
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    • v.1 no.2
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    • pp.84-90
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    • 1990
  • 1,3-Diazatricyclo (5.2.1.Os .to) decane-2,11-dione , C8H10N2O2. MW=166.15, Monoclinic, P2/n a= 6.585(7) , b=9.089(4), c=12.937(10)A, β=95.72(5)˚, V=770.4A3, Z=4, Dc=1.43(4) g/cm3, λ (Mo Ka)=0.7093A, r=1.Ocm-1, T=295˚K, final R=0.037 for 698 unique observed reflections. The compound is the product of the intramolecular (2+2) photocycloaddition of Nl-(w-butenyl)uracil and belongs to a (5.2.1.O5.10) tricyclic system. A pair of molecules related by the inversion symmetry are held together by the strong hydrogen bonding interactions between 02 and H3 of the uracil moiety.

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