Gold Cluster Catalysis: A variety of gold salts and complexes have been used to catalyze different organic reactions. Often, the catalytic rates for these reactions are similar. Oliver-Meseguer et al. (p. 1452 ; see the Perspective by Hashmi ) observed an induction period for the onset of catalysis of organic reactions, such as the ester-assisted hydration of alkynes, for different gold salts and complexes. Mass spectrometry and absorption spectroscopy revealed that small gold clusters (three to ten atoms) formed during these induction periods and are likely to represent the active catalysts. The catalytic reaction rates could be extremely high—up to 10 ⁵ turnovers of the catalyst per hour.

Catalytic hydrogenation of amides is of great interest for chemists working in organic synthesis, as the resulting amines are widely featured in natural products, drugs, agrochemicals, dyes, etc. Compared to traditional reduction of amides using (over)stoichiometric reductants, the direct hydrogenation of amides using molecular hydrogen represents a greener approach. Furthermore, amide hydrogenation is a highly versatile transformation, since not only higher amines (obtained by C–O cleavage), but also lower amines and alcohols, or amino alcohols (obtained by C–N cleavage) can be selectively accessed by fine tuning of reaction conditions. This review describes the most recent advances in the area of amide hydrogenation using H₂exclusively and molecularly defined homogeneous as well as nano-structured heterogeneous catalysts, with a special focus on catalyst development and synthetic applications.

Novel well-defined NNP and PNP manganese pincer complexes have been synthetized and fully characterized. The catalyst Mn-2 containing an imidazolyaminolphosphino ligand shows high activity and selectivity in the hydrogenation of a wide range of secondary and tertiary amides to the corresponding alcohols and amines, under relatively mild conditions. For the first time, more challenging substrates like primary aromatic amides including an actual herbicide can also be hydrogenated using this earth-abundant metal-based pincer catalyst.