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Oxidative rearrangements of tricyclic vinylcyclobutane derivatives

  • Grota, Juliane Fakultät für Chemie, Universität Bielefeld, Germany
  • Mattay, Jochen Fakultät für Chemie, Universität Bielefeld, Germany
  • Piech, Krzysztof Departement de chimie, Université de Fribourg, Switzerland
  • Bally, Thomas Departement de chimie, Université de Fribourg, Switzerland
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  • Chemistry - A European Journal. - 2006, vol. 12, no. 17, p. 4559-4567
English Three tricyclic vinylcyclobutanes (3-methylenetricyclo[,6]decanes 1-3) have been subjected to ionization by photoinduced electron transfer in solution and by X-irradiation in Ar matrices. All three compounds undergo oxidative cycloreversion; the cleavage of the four-membered ring, however, occurs in a different direction depending on the presence of a methyl group in position 6 of the tricyclic framework. In those derivatives, cycloreversion is found to lead to 1-methyl-8-methylene-1,6-cyclodecadiene radical cations (5.⁺ from 1, 8.⁺ from 2) which upon back electron transfer yield two different hydrocarbons (6 from 5.⁺, 9 from 8.⁺), depending on the configuration around the endocyclic double bonds of the respective cyclodecadiene derivative. In the absence of a methyl group on C6, the cycloreversion leads to a radical cation complex between 1-methylenecyclopent-2-ene and cyclopentene (12.⁺) which appears to revert to 3 on back electron transfer. The intermediate radical cations 5.⁺, 8.⁺, and 12.⁺ have been identified and characterized by UV/Vis and IR spectra in Ar matrices. The mechanism of their formation is elucidated by quantum chemical calculations.
Faculté des sciences et de médecine
Département de Chimie
  • English
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