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
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- English
- Classification
- Chemistry
- License
- License undefined
- Identifiers
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- RERO DOC 20346
- DOI 10.1002/chem.201000255
- Persistent URL
- https://folia.unifr.ch/unifr/documents/301685
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