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A one-pot synthesis of 2-aryl- and 2-vinylindoles based on a ruthenium-catalyzed hydroamination and a palladium-catalyzed intramolecular Heck reaction is reported. The ruthenium-catalyzed addition reaction was applied to terminal as well as internal alkynes. Intramolecular Heck reactions of the resulting 2-chloroanilino enamines were achieved using an in situ generated palladium complex derived from an N-heterocyclic carbene.

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.

Air-stable secondary diaminophosphine sulfide preligands enable challenging nickel-catalyzed cross-coupling reactions of electron-deficient as well as electron-rich fluoro(hetero)arenes as electrophiles.

Catalytic amounts of aromatic carboxylic acid MesCO2H enabled efficient ruthenium-catalyzed direct arylations in apolar solvents with unparalleled broad scope via a concerted deprotonation−metalation mechanism.

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.

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.

Two distinct economical catalysts for intramolecular hydroaminations of electronically unactivated alkenes with basic amines are described, which are based on (a) group 4 metal halides under basic reaction conditions or (b) Bronsted-acid organocatalysts.

[reaction: see text] Air-stable and easily accessible PinP(O)H enables highly efficient palladium-catalyzed Kumada cross-coupling reactions of aryl tosylates. The in situ generated catalyst proved applicable not only to electron-rich and electron-poor carbocyclic tosylates but also to heterocyclic tosylates, such as pyridine and quinoline derivatives. The results described herein constitute the first use of air-stable secondary phosphine oxides as preligands for transition-metal-catalyzed coupling reactions between organometallic species and tosylates.

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.

A palladium complex derived from air-stable TADDOLP(O)H catalyzes efficiently Hiyama, Stille, Kumada and Suzuki cross-coupling reactions of aryl and vinyl chlorides.

Two selectively successive I/Cu exchange reactions performed with (Nphyl)CuLi allow the functionalization of indoles in positions 2 and 3. The 2,3-diketones prepared by this method can readily be converted to tricyclic heterocycles by standard methods.