Oxidative rearrangements of tricyclic vinylcyclobutane derivatives

Grota J, Mattay J, Piech K, Bally T (2006)
CHEMISTRY-A EUROPEAN JOURNAL 12(17): 4559-4567.

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Abstract
Three tricyclic vinylcyclobutanes (3-methylenetricyclo[5.3.0.0(2,6)]-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.
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Grota J, Mattay J, Piech K, Bally T. Oxidative rearrangements of tricyclic vinylcyclobutane derivatives. CHEMISTRY-A EUROPEAN JOURNAL. 2006;12(17):4559-4567.
Grota, J., Mattay, J., Piech, K., & Bally, T. (2006). Oxidative rearrangements of tricyclic vinylcyclobutane derivatives. CHEMISTRY-A EUROPEAN JOURNAL, 12(17), 4559-4567.
Grota, J., Mattay, J., Piech, K., and Bally, T. (2006). Oxidative rearrangements of tricyclic vinylcyclobutane derivatives. CHEMISTRY-A EUROPEAN JOURNAL 12, 4559-4567.
Grota, J., et al., 2006. Oxidative rearrangements of tricyclic vinylcyclobutane derivatives. CHEMISTRY-A EUROPEAN JOURNAL, 12(17), p 4559-4567.
J. Grota, et al., “Oxidative rearrangements of tricyclic vinylcyclobutane derivatives”, CHEMISTRY-A EUROPEAN JOURNAL, vol. 12, 2006, pp. 4559-4567.
Grota, J., Mattay, J., Piech, K., Bally, T.: Oxidative rearrangements of tricyclic vinylcyclobutane derivatives. CHEMISTRY-A EUROPEAN JOURNAL. 12, 4559-4567 (2006).
Grota, J, Mattay, Jochen, Piech, K, and Bally, T. “Oxidative rearrangements of tricyclic vinylcyclobutane derivatives”. CHEMISTRY-A EUROPEAN JOURNAL 12.17 (2006): 4559-4567.
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