New Route from Si−O to Si−C Bonds: Alkylalkoxysilanes from Alkoxysilanes and Metal Hydrides

The typical pathway from silicon-oxygen to silicon-carbon bonds involves nucleophilic attack of an organometallic reagent on the silicon center. A new transformation from silicon-oxygen to silicon-carbon bonds is reportedthat proceeds without nucleophilic attack of a carbanion. The reaction of Si(OMe) 4 with NaH yields MeSi(OMe) 3 at temperatures above 300 °C. Mechanistic studies indicate that an intact methyl group is transferred from a methoxy group to the silicon center in the Si-C bond-forming step.