Gold Particles Supported on Amino‐Functionalized Silica Catalyze Transfer Hydrogenation of N‐Heterocyclic Compounds

• Published in: Advanced synthesis & catalysis Vol. 359; no. 4; pp. 677 - 686
• Main Authors: Vilhanová, Beáta, van Bokhoven, Jeroen A., Ranocchiari, Marco
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 20.02.2017; Wiley Subscription Services, Inc
• Subjects: Catalysis; Catalysts; Chemistry; Chemistry, Applied; Chemistry, Organic; Deformation; Deuterium; Disproportionation; Formic acid; Gold; Heterocyclic compounds; Heterogeneous Catalysis; Hydrogen storage; Hydrogenation; Physical Sciences; Quinoline; Saturated N-Heterocycles; Scaffolds; Science & Technology; Silica; Silicon dioxide; Substrates; Synthesis (chemistry); Transfer Hydrogenation; Triethylamine; Gold; HIGHLY SELECTIVE HYDROGENATION; FORMIC-ACID; RUTHENIUM NANOPARTICLES; Heterogeneous Catalysis; Saturated N-Heterocycles; Silica; PALLADIUM NANOPARTICLES; Transfer Hydrogenation; MILD CONDITIONS; ENANTIOSELECTIVE HYDROGENATION; BRONSTED ACID CATALYSIS; ASYMMETRIC HYDROGENATION; HETEROAROMATIC COMPOUNDS
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201601147

In this work we demonstrate that exceptionally small gold particles (d=0.6±0.2 nm) supported on amino‐functionalized mesoporous silicate SBA‐15 are highly active in transfer hydrogenation of structurally diverse unsaturated N‐heterocyclic compounds. The heterocyclic ring is reduced selectively. The gold particles aggregate to a diameter of 4–5 nm in the presence of formic acid/triethylamine (hydrogen donor) during the first catalytic run. In subsequent cycles the nanoparticles maintain their size, yielding a very stable catalytic system that was recycled more than five times. In contrast, analogous SBA catalysts featuring larger (∼5–35 nm) gold particles are not active. Excess formic acid also leads to the formation of formamide derivatives of the products of hydrogenation, which can be deformylated quantitatively. Fifteen structurally different substrates, including the scaffolds of quinoline, isoquinoline, quinoxaline, acridine, phenanthroline, quinazoline, and phenanthridine are hydrogenated and deformylated to give the amine products in >90% overall yield. Deuterium labeling experiments indicate that 1,2‐addition with subsequent disproportionation of the formed intermediate is the preferred reaction path over the 1,4‐addition one, suggesting the participation of a gold hydride species.