Silicon-mediated organic synthesis

Science. 1982 Aug 27;217(4562):793-800. doi: 10.1126/science.217.4562.793.

Abstract

Organic chemists have used the chemical properties of tetracovalent silicon in a remarkable variety of new synthetic transformations. In carbon-functional silanes, exceptional stabilization is provided to a carbocation center in the beta position when the carbon-silicon bond lies in plane. This phenomenon directs electrophilic attack to the silicon-substituted carbon in aryl-, vinyl-, and alkynylsilanes and to carbon-3 in allylsilanes. For different reasons, silicon also stabilizes a carbon-metal bond in the alpha position. Consequently, access to many silicon-containing organometallics is readily available. The exceptional strength of silicon-oxygen and silicon-fluorine bonds is yet another factor that controls the chemical reactivity of silicon reagents. In recent developments, preparative chemists have taken advantage of these properties in imaginative and useful ways.