Cross-metathesis vs. silylative coupling of vinyl alkyl ethers with vinylsilanes catalyzed by a ruthenium–carbene complex (Grubbs catalyst)
- 17 August 2000
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in New Journal of Chemistry
- Vol. 24 (9) , 671-675
- https://doi.org/10.1039/b003442h
Abstract
Grubbs complex, (PCy3)2Cl2RuCHPh (I) is a very effective catalyst of the cross-disproportionation of vinyl-trisubstituted silanes H2CCHSiR3 [where R3=Me3, PhMe2, (OEt)3] with vinyl alkyl ethers H2CCHOR′ [where R′=ethyl, propyl, butyl, t-butyl, t-pentyl, 2-(ethyl)hexyl, cyclohexyl, trimethylsilyl] to yield a mixture of (E+Z) 1-silyl-2-alkoxyethenes. The reaction occurs quantitatively under milder conditions (60°C) than the analogous one catalyzed by Ru–H and/or Ru–Si complexes reported previously (80°C). The stoichiometric reaction of (I) and (PCy3)2Cl2RuCH2 (III) with vinyl ethyl ether leads to the formation of (PCy3)2Cl2RuCH(OEt) (II), inactive in the stoichiometric reaction with vinylsilanes but very active in the catalytic process. Experiments with the use of deuterated vinylsilanes indicate the non-metallacarbene mechanism of the reaction and provide evidence for the initiation of Ru–H bond formation ia the hydrovinylation with vinylsilanes.Keywords
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