Iron-Catalyzed Alkoxylation, Dehydrogenative-Polymerization and Tandem Hydrosilylative-Alkoxylation.

Alkoxylation, hydrosilylative-alkoxylation, and dehydrogenative-polymerization are some of the most widely used transformations in synthetic chemistry. However, these transformations are traditionally catalyzed by precious, and rare late-transition metals. Presented here is a molecularly defined iron complex that catalyzes alkoxylation, tandem hydrosilylative-alkoxylation, and dehydrogenative polymerization of silanes under mild conditions. The iron complex [Fe(CO) (H)(SiPh )] 1 catalyzes a direct Si-O coupling reaction between an array of silanes and alcohols to produce desired alkoxysilanes in excellent yield, with H as the only byproduct. The iron catalyst tolerates various functional groups and provides access to 20 alkoxysilanes, including essential molecules such as β-citronellol and cholesterol. Further, complex 1 catalyzes the polymerization of renewable diol and silane monomer to produce a renewable and degradable poly(isosorbide-silyl ether). Remarkably, complex 1 catalyzes a tandem hydrosilylative-alkoxylation of alkynes under mild conditions to yield unsaturated silyl ethers. The synthetic utility has been demonstrated by gram-scale alkoxylation and hydrosilylative-alkoxylation reactions.