Unlocking the potential of metal ligand cooperation for enantioselective transformations.

Metal-ligand cooperation, in which both the metal and the ligand of a transition metal complex actively participate in chemical transformations leading to enhanced reactivity or selectivity in chemical reactions, has emerged as a powerful and versatile concept in catalysis. This Viewpoint discusses the development trajectory of transition metal-based complexes as catalysts in (de)hydrogenative processes, in particular those cases where metal-ligand cooperation has been invoked to rationalise the observed high reactivities and excellent selectivities. The historical context, mechanistic aspects and current applications are discussed with the suggestion to explore the potential of the MLC mode of action of such catalysts in enantioselective transformations beyond (de)hydrogenative processes.

Catalytic Access to 4-(sec-Alkyl)Anilines via 1,6-Conjugate Addition of Grignard Reagents to Generated aza--Quinone Methides.

The synthesis of aniline derivatives, common building blocks in many pharmaceuticals, agrochemicals, dyes or polymers, has been limited to reactions based on benzene-toluene-xylene derivatives (BTX) due to their ample availability. Despite the large number of existing methodologies, the synthesis of chiral 4-(sec-alkyl)anilines has not been accomplished so far. In this work, a tandem strategy based on the generation of a reactive aza--quinone methide (aza--QM) intermediate followed by Cu(I)-catalyzed addition of Grignard reagents has been developed.

Manganese(i)-catalyzed access to 1,2-bisphosphine ligands.

Chiral bisphosphine ligands are of key importance in transition-metal-catalyzed asymmetric synthesis of optically active products. However, the transition metals typically used are scarce and expensive noble metals, while the synthetic routes to access chiral phosphine ligands are cumbersome and lengthy. To make homogeneous catalysis more sustainable, progress must be made on both fronts.