Synthesis of Arylsilanes by Catalytic Silylation of C(sp ² )─X Bonds: A Review From the Silicon Perspective

ABSTRACT

Arylsilanes constitute an important class of organosilicon compounds with widespread applications in organic synthesis and materials science. Over the past two decades, a range of catalytic synthetic protocols have been developed to access such aromatic organosilanes with increased generality, allowing to forge the C(sp ² )─Si bond through cross‐coupling of various substrate classes with structurally‐diverse silylating reagents. To navigate this synthetic landscape, the present review surveys the key catalytic methodological developments that occurred over the past 15 years for the synthesis of arylsilanes through the silylation of C(sp ² )─X bonds (X =  (pseudo)halide) in functionalized aromatic substrates. Specifically, the field is reviewed from a silicon perspective, where methodologies are categorized and scrutinized according to the philicity (i.e., polarity) of the silylating reagent employed, moving from abundant electrophilic sources (chlorosilanes and hydrosilanes) to more specialized nucleophilic reagents (disilanes, silylboronates, and silylzincs). For each class of reagent, particular emphasis is placed on the structural diversity of the silyl groups that can be successfully transferred to aromatic frameworks.