Ligand design is becoming an increasingly important part of the synthetic activity in chemistry. This is of course because of the subtle control that ligands exert on the metal center to which they are coordinated. Ligands which contain significantly different chemical functionalities, such as hard and soft donors, are often called hybrid ligands and find increasing use in molecular chemistry. Although the interplay between electronic and steric properties has long been recognized as essential in determining the chemical or physical properties of a complex, predictions remain very difficult, not only because of the considerable diversity encountered within the Periodic Table—different metal centers will behave differently towards the same ligand and different ligands can completely modify the chemistry of a given metal—but also because of the small energy differences involved. New systems may—even through serendipity—allow the emergence of useful concepts that can gain general acceptance and help design molecular structures orientated towards a given property. The concept of ligand hemilability, which finds numerous illustrations with hybrid ligands, has gained increased acceptance and been found to be very useful in explaining the properties of metal complexes and in designing new systems for molecular activation, homogeneous catalysis, functional materials, or small‐molecule sensing. In the field of homogeneous enantioselective catalysis, in which steric and/or electronic control of a metal‐mediated process must occur in such a way that one stereoisomer is preferentially formed, ligands containing one or more chiral oxazoline units have been found to be very valuable for a wide range of metal‐catalyzed reactions. The incorporation of oxazoline moieties in multifunctional ligands of increasing complexity makes such ligands good candidates to display hemilabile properties, which until recently, had not been documented in oxazoline chemistry. Herein, we briefly recall the definition and scope of hemilabile ligands, present the main classes of ligands containing one or more oxazoline moieties, with an emphasis on hybrid ligands, and finally explain why the combination of these two facets of ligand design appears particularly promising.

Palladacycle dimers possessing bridging halides can be easily cleaved by using N-heterocyclic carbenes (NHCs) to generate novel monomeric complexes. The structure of one of these was determined by single-crystal diffraction study and consists of a square-planar coordination around the palladium center where the NHC ligand is trans to the amine of the palladacycle. The complex was found to be equally active in aryl amination and alpha-arylation of ketones even at very low catalyst loading (0.02 mol %). Primary and secondary alkyl/arylamines are equally active partners in coupling reactions. [reaction: see text]

R&D issues for the application of Pd-and Ni-catalyzed C À C and C À N coupling reactions in the fine chemicals industry are discussed. In a first part, some background is given on industrial R&D and the role of C À C and C À N coupling for preparative applications is described. The following principal approaches to industrial research are illustrated with relevant examples from the literature and from our own laboratories: i) development of catalysts and catalytic methodologies with industrial potential; ii) finding shorter routes to target molecules using catalytic methods; iii) development of industrial catalytic processes in multi-step syntheses.

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