Biomass-derived ethanol is an important renewable feedstock. Its conversion into high-quality biofuels is a promising route to replace fossil resources. Herein, an efficient manganese-catalyzed Guerbet-type condensation reaction of ethanol to form 1-butanol was explored. This is the first example of upgrading ethanol into higher alcohols using a homogeneous non-noble-metal catalyst. This process proceeded selectively in the presence of a well-defined manganese pincer complex at the parts per million (ppm) level. The developed reaction represents a sustainable synthesis of 1-butanol with excellent turnover number (>110 000) and turnover frequency (>3000 h). Moreover, mechanistic studies including control experiments, NMR spectroscopy, and X-ray crystallography identified the essential role of the "N-H moiety" of the manganese catalysts and the major reaction intermediates related to the catalytic cycle.

Herein, we report a novel cobalt-catalyzed stereodivergent transfer hydrogenation of alkynes to Z- and E-alkenes. Effective selectivity control is achieved based on a rational catalyst design. Moreover, this mild system allows for the transfer hydrogenation of alkynes bearing a wide range of functional groups in good yields using catalyst loadings as low as 0.2 mol %. The general applicability of this procedure is highlighted by the synthesis of more than 50 alkenes with good chemo- and stereoselectivity. A preliminary mechanistic study revealed that E-alkene product was generated via sequential alkyne hydrogenation to give Z-alkene intermediate, followed by a Z to E alkene isomerization process.

Manganese-catalyzed hydrogenation reactions have attracted broad interest since the first report in 2016. Among the reported catalytic systems, Mn catalysts supported by tridentate PNP- and NNP-pincer ligands have most commonly been used. For example, a number of PNP-Mn pincer catalysts have been reported for the hydrogenation of aldehydes, aldimines, ketones, nitriles, and esters. Furthermore, various NNP-Mn pincer catalysts have been shown to be active in the hydrogenation of less-reactive substrates such as amides, carbonates, carbamates, and urea derivations. These observations indicated that Mn catalysts supported by NNP-pincer ligands exhibit higher reactivity in hydrogenation reactions than their PNP counterparts. Such a ligand effect in Mn-catalyzed hydrogenation reactions has yet to be confirmed. Herein, we investigated the origin and applicability of this ligand effect. A combination of experimental and theoretical investigations showed that NNP-pincer ligands on the Mn complexes were more electron-rich and less sterically hindered than their PNP counterparts, leading to higher reactivity in a series of Mn-catalyzed hydrogenation reactions. Inspired by the ligand effect on Mn-catalyzed hydrogenations, we developed the first Mn-catalyzed hydrogenation of N-heterocycles. Specifically, NNP-Mn pincer catalysts hydrogenated a series of N-heterocycles (32 examples) with up to 99% yields, and the corresponding PNP-Mn pincer catalysts afforded low reactivity under the same conditions. This verified that such a ligand effect is generally applicable in hydrogenation reactions of both carbonyl and noncarbonyl substrates based on Mn catalysis.

Herein, we describe a selective cobalt-catalyzed chemodivergent transfer hydrogenation of nitriles to synthesize primary, secondary, and tertiary amines. The solvent effect plays a key role for the selectivity control. The general applicability of this procedure was highlighted by the synthesis of more than 70 amine products bearing various functional groups in high chemoselectivity. Moreover, this mild system achieved >2000 TONs (turnover numbers) for the transfer hydrogenation of nitriles.