Silylative coupling of vinyl alkyl ethers with vinylsilanes catalyzed by ruthenium complexes

Citation
B. Marciniec et al., Silylative coupling of vinyl alkyl ethers with vinylsilanes catalyzed by ruthenium complexes, ORGANOMETAL, 19(9), 2000, pp. 1677-1681
Citations number
20
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
ORGANOMETALLICS
ISSN journal
0276-7333 → ACNP
Volume
19
Issue
9
Year of publication
2000
Pages
1677 - 1681
Database
ISI
SICI code
0276-7333(20000501)19:9<1677:SCOVAE>2.0.ZU;2-2
Abstract
Ruthenium complexes such as RuHCl(CO)(PPh3)(3) (I), RuCl(SiMe3)(Co)(PPh3)(2 ) (II), RuCl2- (PPh3)(3) (III), and Ru(CO)(3)(PPh3)(2) (IV) appear to be ve ry effective catalysts of cross-disproportionation of vinyl-trisubstituted silanes CH2=CHSiR3 (where R-3 = Me-3, PhMe2, (OEt)(3)) with vinyl alkyl eth ers CH2=CHOR' (where R' = ethyl, n-propyl, n-butyl, tert-butyl, tert-pentyl , 2-ethylhexyl, cyclohexyl, trimethylsilyl) to yield a mixture (E+Z) of 1-s ilyl-2-alkoxyethenes. Stoichiometric insertion of vinyl n-propyl ether into Ru-Si bonds of II and MS study of the products of the deuterated vinyltrim ethylsilane with vinyl ethyl ether indicate that the mechanism of cross-dis proportionation involves a migratory insertion of the vinyl ether into the Ru-Si bond (and vinylsilane into the Ru-H bond) followed by beta-H (and P-S i) transfer to eliminate 1-triorganosilyl-2-alkoxyethenes (and ethene).