Journal article
+ 2 other files
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
Show more…
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
-
-
Classification
-
Chemistry
-
License
-
License undefined
-
Identifiers
-
-
Persistent URL
-
https://folia.unifr.ch/unifr/documents/301685
Other files
Statistics
Document views: 134
File downloads:
- bal_ror.pdf: 138
- bal_ror_sm2.txt: 101
- bal_ror_sm3.txt: 35