Selective Homogeneous Hydrogenation of Biogenic Carboxylic Acids with [Ru(TriPhos)H]+: A Mechanistic Study

Abstract

Selective hydrogenation of biogenic carboxylic acids is an important transformation for biorefinery concepts based on platform chemicals. We herein report a mechanistic study on the homogeneously ruthenium/phosphine catalyzed transformations of levulinic acid (LA) and itaconic acid (IA) to the corresponding lactones, diols, and cyclic ethers. A density functional theory (DFT) study was performed and corroborated with experimental data from catalytic processes and NMR investigations. For [Ru(TriPhos)H]⁺ as the catalytically active unit, a common mechanistic pathway for the reduction of the C═O functionality in aldehydes, ketones, lactones, and even free carboxylic acids could be identified. Hydride transfer from the Ru–H group to the carbonyl or carboxyl carbon is followed by protonation of the resulting Ru–O unit via σ-bond metathesis from a coordinated dihydrogen molecule. The energetic spans for the reduction of the different functional groups increase in the order aldehyde < ketone < lactone ≈ carboxylic acid. This reactivity pattern as well as the absolute values are in full agreement with experimentally observed activities and selectivities, forming a rational basis for further catalyst development.