Palladium-catalyzed coupling of functionalized primary and secondary amines with aryl and heteroaryl halides: two ligands suffice in most cases

Palladium-Catalyzed Coupling of Functionalized Primary and Secondary Amines with Aryl and Heteroaryl Halides: Two Ligands Suffice in Most Cases.

We report our studies on the use of two catalyst systems, based on the ligands BrettPhos (1) and RuPhos (2), which provide the widest scope for Pd-catalyzed C-N cross-coupling reactions to date. Often low catalyst loadings and short reaction times can be used with functionalized aryl and heteroaryl coupling partners. The reactions are highly robust and can be set up and performed without the us...

Highly Selective Palladium-Catalyzed Cross-Coupling of Secondary Alkylzinc Reagents with Heteroaryl Halides

The highly selective palladium-catalyzed Negishi coupling of secondary alkylzinc reagents with heteroaryl halides is described. The development of a series of biarylphosphine ligands has led to the identification of an improved catalyst for the coupling of electron-deficient heterocyclic substrates. Preparation and characterization of oxidative addition complex (L)(Ar)PdBr provided insight into...

Palladium-catalyzed aminations of aryl halides with phosphine-functionalized imidazolium ligands.

A series of 1-(2-diphenylphosphinoferrocenyl)ethyl-3-substituted imidazolium iodides [3-substituent = methyl (1a); isopropyl (1b); tert-butyl (1c); 1-adenosyl (1d); cyclohexyl (1e); 2,6-dimethylphenyl (1f); 2,4,6-trimethylphenyl (1g); 2,6-diisopropylphenyl (1h)] have been prepared and evaluated as ligands in the palladium-catalyzed aminations of aryl halides with various amines. The scope of th...

Palladium-Catalyzed Hydroxylation of Aryl and Heteroaryl Halides Enabled by the Use of a Palladacycle Precatalyst

A method for the hydroxylation of aryl and heteroaryl halides, promoted by a catalyst based on a biarylphosphine ligand tBuBrettPhos (L5) and its corresponding palladium precatalyst (1), is described. The reactions allow the cross-coupling of both potassium and cesium hydroxides with (hetero)aryl halides to afford a variety of phenols and hydroxylated heteroarenes in high to excellent yield.

General preparation of primary, secondary, and tertiary aryl amines by the oxidative coupling of polyfunctional aryl and heteroaryl amidocuprates.