期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 48, 页码 17307-17311出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201911282
关键词
alkenes; density functional calculations; homogeneous catalysis; silylium ions; Si-Si activation
资金
- Alexander von Humboldt Foundation
- Berlin Graduate School of Natural Sciences and Engineering
- Deutsche Forschungsgemeinschaft
- Einstein Foundation (Berlin)
A metal-free, intermolecular syn-addition of hexamethyldisilane across simple alkenes is reported. The catalytic cycle is initiated and propagated by the transfer of a methyl group from the disilane to a silylium-ion-like intermediate, corresponding to the (re)generation of the silylium-ion catalyst. The key feature of the reaction sequence is the cleavage of the Si-Si bond in a 1,3-silyl shift from silicon to carbon. A central intermediate of the catalysis was structurally characterized by X-ray diffraction, and the computed reaction mechanism is fully consistent with the experimental findings.
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