- ?-Silicon-effect-promoted intermolecular site-selective C(sp3)-H amination with dirhodium nitrenes
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A dirhodium-catalyzed, ?-selective C-H amination of organosilicon compounds has been developed. Primary C(sp3)-H bonds of silylethyl groups and secondary C(sp3)-H bonds of silacycloalkanes can be selectively converted to C-N bonds at the ?-position of the silicon atoms. The experimental data and theoretical calculations indicate that the strong s-donor ability of the carbon-silicon bonds is responsible for the ?-selectivity. Kinetic isotope effects clearly demonstrate that the C-H bond cleavage step is not turnover-limiting, but selectivity-determining.
- Ninomiya, Ryo,Arai, Kenta,Chen, Gong,Morisaki, Kazuhiro,Kawabata, Takeo,Ueda, Yoshihiro
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supporting information
p. 5759 - 5762
(2020/06/03)
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- SYNTHETIC PROCESS FOR CYCLIC ORGANOSILANES
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A process for preparing a cyclic organosilane using a solvent that promotes ring-closure reactions between an organosilane compound and a dihalo organic compound is disclosed. The ring-closure reactions may form a 4-, 5- or 6-member cyclic organosilane. The process involves a mixture including a dihalo organic compound, an organosilane having at least two functional groups, a solvent and magnesium (Mg). The two functional groups in the organosilane may include halogen, alkoxy or a combination thereof. In the presence of Mg, a Grignard intermediate is formed from the dihalo organic compound in the mixture. The solvent favors intra-molecular or self-coupling reactions of the Grignard intermediate. The intra-molecular or self-coupling reaction promotes ring-closure reaction of the Grignard intermediate to form the cyclic organosilane.
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Page/Page column 16-17
(2008/06/13)
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- UEBER DIE AUSTAUSCHBARKEIT VON METHYL- UND PHENYLGRUPPEN AM SILICIUM VON SILACYCLOPENTAN BEI DER EINWIRKUNG VON ALKYL- UND ARYLLITHIUMVERBINDUNGEN IN DIETHYLETHER ODER TETRAHYDROFURAN
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A degenerate ligand exchange, presumably via an ate-complex intermediate, takes place upon treatment of 1,1-dimethyl- (3) and 1,1-diphenyl-silacyclopentane (17) in THF-d8 with perdeuteriomethyllithium (4-d3) or perdeuteriophenyllithium (15-d5), respective
- Maercker, Adalbert,Stoetzel, Reinhard
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p. C57 - C63
(2007/10/02)
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