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A palladium complex derived from a sterically hindered diaminochlorophosphine allowed for Suzuki-Miyaura cross-couplings of chloroarenes with ample scope and provided access to tetra-ortho-substituted bi(hetero)aryls.

Catalytic amounts of economically attractive [RuCl3(H2O)n] allow for direct arylations via C–H bond functionalization with aryl bromides under phosphine ligand-free reaction conditions. Thereby, a variety of functionalized (hetero)aryl bromides, bearing either electron-withdrawing or electron-releasing substituents, can be employed for direct arylations of pyridine, oxazoline, pyrazole, or ketimine derivatives as pronucleophiles.

Generally applicable, palladium-catalyzed direct arylations of 1,2,3-triazoles with aryl chlorides were accomplished through conventional heating at reaction temperatures of 105-120 °C. Thereby, intra-and intermolecular C-H bond functionalizations were achieved with a variety of differently substituted chlorides as electrophiles, bearing numerous valuable functional groups.

Catalytic amounts of [RuCl 3 (H 2 O) n ] allow for direct -arylations via C-H bond functionalization with aryl bromides, -bearing a variety of important functional groups.

Studies on the use of easily accessible heteroatom-substituted secondary phosphine oxides as preligands for cross-coupling reactions are described. These air-stable sterically hindered phosphine oxides allow for efficient palladium-catalyzed Suzuki- and nickel-cat- alyzed Kumada-coupling reactions using electronically deactivated aryl chlorides. In addi- tion, they enable nickel-catalyzed coupling reactions of magnesium organyls with aryl fluo- rides at ambient temperature, and ruthenium-catalyzed coupling reactions of aryl chlorides via C-H bond activation. Finally, the application of modular diamino phosphine chlorides as preligands for a variety of transition-metal-catalyzed C-C and C-N bond formation reactions employing electron-rich aryl chlorides is presented.