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Vinyl Tris(trimethylsilyl)silanes: Substrates for Hiyama Coupling.

ABSTRACT: The oxidative treatment of vinyl tris(trimethylsilyl)silanes with hydrogen peroxide in aqueous sodium hydroxide in tetrahydrofuran generates reactive silanol or siloxane species that undergo Pd-catalyzed cross-couplings with aryl, heterocyclic and alkenyl halides in the presence of Pd(PPh(3))(4) and tetrabutylammonium fluoride. Hydrogen peroxide and base are necessary for the coupling to occur while activation of the silanes with fluoride is not required. The conjugated and unconjugated tris(trimethylsilyl)silanes serve as good cross-coupling substrates. The (E)-silanes undergo coupling with retention of stereochemistry while coupling of (Z)-silanes occurred with lower stereoselectivity to produce an E/Z mixture of products.

SUBMITTER: Wang Z

PROVIDER: S-EPMC2430103 | biostudies-literature | 2008 May

REPOSITORIES: biostudies-literature

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Vinyl Tris(trimethylsilyl)silanes: Substrates for Hiyama Coupling.

Wang Zhizhong Z Pitteloud Jean-Philippe JP Montes Lucresia L Rapp Magdalena M Derane Djenny D Wnuk Stanislaw F SF

Tetrahedron 20080501 22

The oxidative treatment of vinyl tris(trimethylsilyl)silanes with hydrogen peroxide in aqueous sodium hydroxide in tetrahydrofuran generates reactive silanol or siloxane species that undergo Pd-catalyzed cross-couplings with aryl, heterocyclic and alkenyl halides in the presence of Pd(PPh(3))(4) and tetrabutylammonium fluoride. Hydrogen peroxide and base are necessary for the coupling to occur while activation of the silanes with fluoride is not required. The conjugated and unconjugated tris(tri ...[more]

PMID: 19478830

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