Journal article
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Regioselective oxidative ring opening of cyclopropyl silyl ethers: a quantum chemical study
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Rinderhagen, Heiko
Department of Chemistry, Bielefeld University, Germany - CILAG AG, Schaffhausen, Switzerland
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Mattay, Jochen
Department of Chemistry, Bielefeld University, Germany
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Nussbaum, Rafael
Department of Chemistry, University of Fribourg, Switzerland
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Bally, Thomas
Department of Chemistry, University of Fribourg, Switzerland
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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.
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Faculty
- Faculté des sciences et de médecine
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Department
- Département de Chimie
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Language
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Classification
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Chemistry
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License
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License undefined
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Identifiers
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Persistent URL
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https://folia.unifr.ch/unifr/documents/301685
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