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.