Breaking the Base Barrier: Cu(II)-Mediated C-H Heteroarylation of o-Carboranes with Base-Sensitive Heteroaryl Halides.

While cage C-arylation reactions using strong bases are among the most frequently used transformations in carborane chemistry, there has been no general solution to allow for the use of weak bases in the reaction. Moreover, base-metal-promoted C-H heteroarylation with base-sensitive heteroaryl halides remained elusive. Herein, copper-mediated cage C-H (hetero)arylation has been achieved without the need for strong bases, leading to the facile synthesis of a wide range of C-(hetero)arylated carboranes in good to excellent yields with a broad substrate scope and good functional group compatibility.

Pd-Catalyzed Oxidative Dehydrogenative Cross Coupling of Cage B-H/B-H Bonds at Room Temperature: Synthesis of Bis(o-carborane)s.

Efficient Pd-catalyzed oxidative dehydrogenative cross coupling of B-H/B-H bonds of two pyridyl o-carboranes has been developed, leading to the preparation of B(3)-B(6') heterocoupled and B(3)-B(6') homocoupled biscarboranes with a broad substrate scope at room temperature.

Pd-Catalyzed Selective B(6)-H Phosphorization of nido-Carboranes via Cascade Deboronation/B-H Activation from closo-Carboranes.

Efficient Pd-catalyzed regioselective B(6)-H phosphorization of nido-carboranes via cascade deboronation/B-H activation of readily available C-substituted o-carboranes with various phosphines using 3-methylpyridine or isoquinoline as a directing group in combination with pyridine ligands has been developed, affording unprecedented B(6)-phosphinated nido-carborane derivatives with high selectivity in a simple one-pot process.

Palladium-Catalyzed Regioselective B(3,4)-H Acyloxylation of o-Carboranes.

We disclose herein an efficient regioselective B(3,4)-H activation via a ligand strategy, affording B(3)-monoacyloxylated and B(3,4)-diacyloxylated o-carboranes. The identification of amino acid and phosphoric acid ligands is crucial for the success of B(3)-mono- and B(3,4)-diacyloxylation, respectively. This ligand approach is compatible with a broad range of carboxylic acids. The functionalization of complex drug molecules is demonstrated. Other acyloxyl sources, including sodium benzoate, benzoic anhydride, and iodobenzene diacetate, are also tolerated.

Palladium-catalyzed selective B(3)-H arylation of o-carboranes with arylboronic acids at room temperature.

A palladium-catalyzed selective B(3)-H arylation of o-carboranes at room temperature has been developed using readily available arylboronic acids as the aryl source, and the corresponding 3-aryl-o-carboranes were obtained in good to excellent yields. This method provides a powerful synthetic route for constructing polysubstituted o-carborane derivatives.

Transition-metal-free direct nucleophilic substitution of carboranyllithium and 2-halopyridines.

A practical and efficient C(cage)-heteroarylation of carborane is presented, via direct nucleophilic substitution of carboranyllithium with 2-halopyridines. This reaction does not need the aid of any transition metal and utilizes readily available carboranyllithium nucleophiles, thereby avoiding transmetalation of carboranyllithium. The process exhibits a broad scope, and a vast array of 2-halopyridines have proven to be suitable substrates. The method serves as a complement to C(cage)-arylation reactions and may find wide applications in materials science and medicinal and coordination chemistry.

Copper-catalyzed synthesis of 2-aminopyridylbenzoxazoles via domino reactions of intermolecular N-arylation and intramolecular O-arylation.

A simple and general approach to nitrogen-containing heterocycles via copper-catalyzed domino reaction has been developed, and the corresponding 2-aminopyridylbenzoxazole derivatives were obtained in good to excellent yields using the readily available starting materials. This method possesses unique step economy features, and is of high tolerance towards various functional groups in the substrates.

Palladium-Catalyzed Direct Cross-Coupling of Carboranyllithium with (Hetero)Aryl Halides.

A palladium-catalyzed direct C-arylation reaction of readily available cage carboranyllithium reagents with aryl halides has been developed for the first time. This method is applicable to a wide range of aryl halide substrates including aryl iodides, aryl bromides, and heteroaromatic halides.