A metal‐catalyzed methylation process has been developed. By employing an air‐ and moisture‐stable manganese catalyst together with isotopically labeled methanol, a series of D‐, CD3‐, and 13C‐labeled products were obtained in good yields under mild reaction conditions with water as the only byproduct.

The first base metal catalyzed transfer hydrogenation of alkynes with methanol is described. An air and moisture stable manganese pincer complex catalyzes the reduction of a variety of different alkynes to the corresponding (Z)-olefins in high yields. The reaction is stereo-and chemoselective and scalable.

A general and chemoselective catalytic alkylation of nitriles using a homogeneous nonprecious manganese catalyst is presented. This alkylation reaction uses naturally abundant alcohols and readily available nitriles as coupling partners. The reaction tolerates a wide range of functional groups and heterocyclic moieties, efficiently providing useful cyanoalkylated products with water as the only side product. Importantly, methanol can be used as a C1 source and the chemoselective C-methylation of nitriles is achieved. The mechanistic investigations support the multiple role of the metal− ligand manganese catalyst, the dehydrogenative activation of the alcohol, α-C−H activation of the nitrile, and hydrogenation of the in-situ-formed unsaturated intermediate.

The nucleophilic addition to nitrogen in 3-monosubstituted s-tetrazines under mild conditions is reported, by using silyl-enol ethers as the nucleophiles and mediated by BF 3 . The preference for this azaphilic addition over the usually observed inverse electron demand Diels-Alder reactions was determined experimentally and evaluated theoretically. In this regard, the influence of the effect of BF 3 -coordination to s-tetrazines was investigated thoroughly. The substrate dependency of this unusual reaction was rationalized by determination of the activation barriers and on the basis of the activation strain model by employing density functional theory. Lastly, the decomposition of the unstable adducts was examined and an interesting rearrangement to a triazine derived structure was observed.

A highly selective hydrogenation of alkynes using an air stable and readily available manganese catalyst has been achieved. The reaction proceeds under mild reaction conditions and tolerates various functional groups resulting in (Z)-alkenes and allylic alcohols in high yields. Mechanistic experiments suggest that the reaction proceeds via a bifunctional activation involving metal-ligand cooperativity.