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)4 (H)(SiPh3 )] 1 catalyzes a direct Si-O coupling reaction between an array of silanes and alcohols to produce desired alkoxysilanes in excellent yield, with H2 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.