Catalytic Disproportionation of Formic Acid to Methanol by using Recyclable Silylformates.

A novel strategy to prepare methanol from formic acid without an external reductant is presented. The overall process described herein consists of the disproportionation of silyl formates to methoxysilanes, catalyzed by ruthenium complexes, and the production of methanol by simple hydrolysis. Aqueous solutions of MeOH (>1 mL, >70 % yield) were prepared in this manner. The sustainability of the reaction has been established by recycling of the silicon-containing by-products with inexpensive, readily available, and environmentally benign reagents.