Silylative Coupling of Olefins with Vinylsilanes in the Synthesis of π‐Conjugated Double Bond Systems

Abstract

The design and development of highly efficient and selective methods for the synthesis of π‐conjugated arylvinyl derivatives, based on sequential catalytic reactions of organometallic reagents, have been the subject of extensive study because of their versatile application in organic synthesis and materials science. The silylative coupling of olefins with vinyl‐substituted silicon compounds represents one of the most efficient and selective methods for the synthesis of alkenylsilanes, which are particularly attractive scaffolds for further transformations, including transition‐metal‐catalysed cross‐coupling with organic halides or substitution with organic and inorganic electrophiles. The microreview highlights recent developments in sequential synthetic strategies including ruthenium‐catalysed silylative coupling followed by desilylative cross‐coupling and halogenation, leading to stereodefined organic derivatives containing arylene‐vinylene units widely applied as fine chemicals, functional materials or unsaturated building blocks in organic synthesis.

Nickel-Catalyzed C–H Silylation of Arenes with Vinylsilanes: Rapid and Reversible β-Si Elimination

“…To investigate if C–H bond activation was occurring, C 6 F 5 D and H 2 CCHSi­(OEt) 3 were reacted with a catalytic amount of Ni­(COD) 2 and i Pr 2 Im and heated at 120 °C for 12 h. The 19 F­{ 1 H} NMR showed deuterium exchange into the arene indicating that C–H activation still readily occurs, and so it is likely that the β-Si elimination step is not viable with the Si­(OEt) 3 substituent. Although limited information is known about the propensity of silyl groups to undergo β-Si elimination, this result is consistent with previous studies on Ru complexes . The SiBnMe 2 substituent, where Bn = benzyl, has also found use in coupling reactions and seemed more likely to be capable of β-Si elimination .…”

Fe and Co Complexes of Rigidly Planar Phosphino-Quinoline-Pyridine Ligands for Catalytic Hydrosilylation and Dehydrogenative Silylation

“…The finding that the Co- iPr PQpy catalysts were active for dehydrogenative silylation (Table ) led to an investigation of their use for producing vinylsilanes from silanes and ethylene. Vinylsilanes are versatile reagents, as they can be polymerized, undergo alkene metathesis, are amenable to hydrosilylation, and serve as vinyl transfer agents. − Vinylsilanes are prepared by hydrosilylation of acetylene as well as reaction of vinyl lithium with silyl halides. , Dehydrogenative silylation has rarely been applied to their preparation . It is known that ethylene and HSi­(OEt) 3 react to give EtSi­(OEt) 3 , , but the conversion to CH 2 CHSi­(OEt) 3 would be of greater interest…”

Silylative coupling of olefins with vinylsilanes in the synthesis of functionalized alkenes

“…The silylative coupling, in combination with subsequent desilylation reactions such as Hiyama cross-coupling and halodesilylation, appears to be a valuable step to provide functionalized unsaturated organic compounds. 35 The article highlights the recent developments in the sequential synthetic strategies including ruthenium-catalyzed silylative coupling followed by desilylative cross-coupling, acylation and halogenation, leading to stereodefined organic derivatives containing arylene-vinylene units which are widely applied as fine chemicals, functional materials or unsaturated building blocks in organic synthesis.…”