Mechanochemical Metal-Free Transfer Hydrogenation of Carbonyls Using Polymethylhydrosiloxane as the Hydrogen Source

Abstract

We report herein a new methodology for the rapid and selective reduction of carbonyls in the solid phase. By exploiting mechanical energy and using a cheap and air-stable silane, polymethylhydrosiloxane (PMHS), we can reduce a variety of carbonyl compounds, with catalytic amounts of fluorides. A scope of 19 substrates was explored to probe the generality of the method. In addition, an important biomass-based platform chemical, 5-hydroxymethylfurfural (5-HMF), and an insoluble polymer, polyketone, could be reduced with this methodology. A mechanistic study is also presented, suggesting the active role of volatile silane species. This method is particularly appealing to overcome substrate solubility issues and reduce solvent reliance in organic synthesis.