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
-
2006
Published in:
- Chemistry - A European Journal. - 2006, vol. 12, no. 17, p. 4559-4567
cycloreversion
matrix isolation
photoinduced electron transfer
quantum chemical calculations
radical ions
English
Three tricyclic vinylcyclobutanes (3-methylenetricyclo[5.3.0.02,6]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.
- Faculty
- Faculté des sciences et de médecine
- Department
- Département de Chimie
- Language
-
- English
- Classification
- Chemistry
- License
- License undefined
- Identifiers
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- RERO DOC 5731
- DOI 10.1002/chem.200501338
- Persistent URL
- https://folia.unifr.ch/unifr/documents/300137
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