期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 16, 期 24, 页码 7121-7124出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201000255
关键词
cations; cyclopropyl ethers; electron transfer; radicals; potential surfaces
资金
- Studienstiftung des Deutschen Volkes
- DFG
- Swiss National Science Foundation [200020121747]
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(OTMS) 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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