915377-72-9Relevant academic research and scientific papers
Competition of insertion and transmetalation pathways in the reactions of alkenylsilanes with aryl complexes of palladium(II). An experimental study
Albeniz, Ana C.,Espinet, Pablo,Lopez-Fernandez, Raquel
, p. 5449 - 5455 (2006)
Reactions of alkenylsilanes (alkenyl = 2-propenyl, vinyl, allyl) with neutral and cationic palladium aryl complexes [Pd(C6F 5)X(NCMe)2] (X = Br, 1; Cl, 2), [Pd(C6F 5)(acac)(NCMe)] (acac = acetylacetonate, 3), and [Pd(C 6F5)(bipy)(S)]ClO4 (S = acetone, 4) were studied. The compounds obtained were substituted alkenylsilanes (formed via Heck substitution) and desilylated olefins (formed by transmetalation followed by reductive elimination or by insertion followed by β-SiMe3 elimination). The analysis of the structure of the final organic products provides a quantitative assessment of the importance of these competing pathways. Transmetalation to palladium was found to be a minor pathway in all cases, whereas insertion of the double bond into the Pd-C6F 5 bond followed by β-SiMe3 elimination was the major route. The formation of C6F5-substituted alkenylsilanes is favored when an excess of starting alkenylsilane is used.
