Catalytic Disproportionation of Formic Acid to Methanol by using Recyclable Silylformates

Abstract

A novel strategy to prepare methanol from formic acid without external reductant is presented. The overall process described herein consists in the disproportionation of silyl formates to methoxysilanes catalyzed by ruthenium complexes and the production of methanol thereof 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 the recycling of the silicon-containing byproducts with cheap, readily available and environmentally-benign reagents.

Silyl formates as hydrosilane surrogates for the transfer hydrosilylation of ketones

“…As we previously reported, an initial decarbonylation of silyl formate 5 on catalyst 2 generates the active catalyst ruthenium formate A, which through decarboxylation leads to the ruthenium hydride species B. [18] The presence of a ruthenium hydride species was confirmed by NMR analysis of the reaction mixture (see supporting information, Figures S8 and S9). Interaction of ketone 3 with the ruthenium-hydride complex B results in its reduction, presumably assisted by a hydrogen bond formed between the carbonyl group and the ligand PN H P (C) [19] .…”

Silyl formates as hydrosilane surrogates for the transfer hydrosilylation of ketones

“…As we previously reported, an initial decarbonylation of silyl formate 5 on catalyst 2 generates the active catalyst ruthenium formate A , which through decarboxylation leads to the ruthenium hydride species B . 18 The presence of a ruthenium hydride species was confirmed by NMR analysis of the reaction mixture (see Fig. S8 and S9, ESI†).…”