Dehydrogenative oxidation of hydrosilanes using gold nanoparticle deposited on citric acid-modified fibrillated cellulose: unveiling the role of molecular oxygen.

Efficient and environmentally friendly synthesis of silanols is a crucial issue across the broad fields of academic and industrial chemistry. Herein, we describe the dehydrogenative oxidation of hydrosilane using a gold nanoparticle catalyst supported by fibrillated citric acid-modified cellulose (F-CAC). Au:F-CAC catalysts with various particle sizes (1.7 nm, 4.9 nm, and 7.7 nm) were prepared using the trans-deposition method, a technique previously reported by our group. These catalysts exhibited significant catalytic activity to produce silanols with high turnover frequency (TOF) of up to 7028 h-1. Recycling experiments and transmission electron microscopy (TEM) observation represented the high durability of Au:F-CAC under the reaction conditions, allowing kinetic studies on size dependency. Mechanistic studies were conducted, including isotope labelling experiments, kinetics, and various spectroscopies. Notably, the near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) of the model catalyst (Au:PVP) revealed the formation of catalytically active cationic Au sites on the surface through the adsorption of molecular oxygen, providing a new insight into the reaction mechanism.

Intramolecular hydroamination catalysed by gold nanoparticles deposited on fibrillated cellulose.

Gold nanoparticles stabilised by fibrillated citric acid-modified cellulose (Au:F-CAC) catalyse the intramolecular cycloamination of amines to unactivated alkenes under an aerobic atmosphere to afford pyrrolidine derivatives. Only 0.2 mol% of Au loading is required to complete the reaction. The high sensitivity of the Au:F-CAC catalyst to the substitution pattern of alkenes allows a unique chemoselective cycloamination, affording new compounds.