Abstract
The combination of electrophilic and nucleophilic reaction partners can be an obvious approach toward the formation of C(sp(3))-Si bonds. Regioselectivity issues are avoided as the locus of bond formation is set in the prefunctionalized alkyl coupling partner. However, synthetically useful protocols only evolved in recent years, closing an important gap in silicon chemistry. This Perspective summarizes early efforts for the construction of C(sp(3))-Si bonds and highlights the recent catalytic approaches either utilizing electrophilic or nucleophilic silicon reagents. The underlying reaction mechanisms range from ionic or radical cross-couplings to simple nucleophilic substitution.