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Regioselective oxidative ring opening of cyclopropyl silyl ethers: a quantum chemical study

  • Rinderhagen, Heiko Department of Chemistry, Bielefeld University, Germany - CILAG AG, Schaffhausen, Switzerland
  • Mattay, Jochen Department of Chemistry, Bielefeld University, Germany
  • Nussbaum, Rafael Department of Chemistry, University of Fribourg, Switzerland
  • Bally, Thomas Department of Chemistry, University of Fribourg, Switzerland
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    10.05.2010
Published in:
  • Chemistry, a European Journal. - 2010, vol. 16, no. 24, p. 7121–7124
English In contrast to the structurally and configurationally stable alkyl- or aryl-substituted cyclopropyl radical cations, cyclopropyl silyl ethers undergo spontaneous ring opening upon oxidation whereby the endocyclic C-C(O-TMS) bond is cleaved with remarkable selectivity. DFT calculations on 1-trimethylsilyloxybicyclo[4.1.0]heptane show that this selectivity arises from the topology of the potential surface of the corresponding radical cation which is initially generated in a very steep region of the potential surface from where the steepest descent leads to cleavage of the endocyclic rather than the lateral C-C(OTMS) bond. Cleavage of the lateral bond leads to interesting conformational changes which are explored in detail.
Faculty
Faculté des sciences et de médecine
Department
Département de Chimie
Language
  • English
Classification
Chemistry
License
License undefined
Identifiers
Persistent URL
https://folia.unifr.ch/unifr/documents/301685
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