The selective, direct hydrogenation of amides to the corresponding alcohols and amines with cleavage of the C-N bond was discovered. The expected products of C-O cleavage are not formed (except as traces in the case of anilides). The reaction proceeds under mild pressure and neutral, homogeneous conditions using a dearomatized, bipyridyl-based PNN Ru(II) pincer complex as a catalyst. The postulated mechanism involves metal-ligand cooperation by aromatization-dearomatization of the heteroaromatic pincer core and does not involve hydrolytic cleavage of the amide. The simplicity, generality, and efficiency of this environmentally benign process make it attractive for the direct transformations of amides to alcohols and amines in good to excellent yields.

A clean sweep: Aryl and aliphatic imines can be synthesized directly and efficiently from alcohols and amines under mild, neutral conditions with the liberation of only molecular hydrogen and water (see scheme; R=isopropyl, tert‐butyl). This general, environmentally benign reaction is catalyzed by a de‐aromatized ruthenium PNP pincer complex (0.2 mol %), and can proceed in toluene under an inert atmosphere or under air.

The acridine-based pincer complex 1 exhibits an unprecedented mode of metal-ligand cooperation involving a "long-range" interaction between the distal acridine C9 position and the metal center. Reaction of 1 with H(2)/KOH results in H(2) splitting between the Ru center and C9 with concomitant dearomatization of the acridine moiety. DFT calculations show that this process involves the formation of a Ru dihydride intermediate bearing a bent acridine ligand in which C9 is in close proximity to a hydride ligand followed by through-space hydride transfer. Ammonia induces transfer of a hydride from the Ru center of 1 to C9 of the flexible acridine pincer ligand, forming an unusual dearomatized fac-acridine PNP complex.

Efficient synthesis of amides directly from esters and amines is achieved under mild, neutral conditions with the liberation of molecular hydrogen. Both primary and secondary amines can be utilized. This unprecedented, general, environmentally benign reaction is homogeneously catalyzed under neutral conditions by a dearomatized ruthenium-pincer PNN complex and proceeds in toluene under an inert atmosphere with a high turnover number (up to 1000). PNP analogues do not catalyze this transformation, underlining the crucial importance of the amine arm of the pincer ligand. A mechanism is proposed involving metal-ligand cooperation via aromatization-dearomatization of the pyridine moiety and hemilability of the amine arm.

Transition metal and reductant free α-C(sp3)-H hydroxylation of carbonyl compounds are reported. This method is promoted by commercially available inexpensive KO-t-Bu and atmospheric air as an oxidant at room temperature. This unified strategy is also very facile for hydroxylation of various carbonyl compound derivatives to obtain quaternary hydroxyl compounds in excellent yield. A preliminary mechanistic investigation, supported by isotope labeling and computational studies, suggests the formation of a peroxide bond and its cleavage by in situ generated enolate.

The amide functional group is commonly found in peptides, proteins, pharmaceutical compounds, natural products, andp olymers.T he synthesis of amides is typically performed by using classical approaches that involvet he reaction between ac arboxylic acid and an amine in the presence of an activator.Amides are thought to be an inert functional group, because they are unsusceptible to nucleophile attack, owing to their low electrophilicity.T he reason fort his resistancei sc lear:t he resonance stability of the amide bond. However,t ransition metal catalysis can circumvent this stability by selectively rupturing the NÀCb ond of the amide, thereby facilitating further cross-couplingo ro ther reactions.Inthis Focus Review,wediscuss the recent advances in this area and present as ummary of methods that have been developed for activating the amide NÀCb ond by using precious and non-preciousmetals.

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Sauber und direkt: Aromatische und aliphatische Imine können unter milden, neutralen Bedingungen direkt und effizient aus Alkoholen und Aminen hergestellt werden (siehe Schema; R=Isopropyl, tert‐Butyl). Diese universelle, umweltverträgliche Reaktion wird durch einen desaromatisierten Ruthenium‐PNP‐Pinzettenkomplex katalysiert (0.2 Mol‐%) und kann in Toluol unter Inertgas oder an Luft ausgeführt werden.