Transition-Metal-Free Intermolecular Hydrocarbonation of Styrenes Mediated by NaH/1,10-Phenanthroline.

A transition-metal-free intermolecular coupling reaction of halocompounds with styrenes in the presence of NaH and 1,10-phenanthroline was developed. This reaction afforded hydrocarbonated products with complete anti-Markovnikov selectivity. The method allows the use of a wide range of halocompounds, including aryl and alkyl halides, and good functional group tolerance. Detailed mechanistic studies indicated that an anilide anion generated in situ by the NaH-mediated reduction of 1,10-phenanthroline works as an electron donor and a hydrogen source.

NaH-mediated direct C-H arylation in the presence of 1,10-phenanthroline.

Transition-metal-free coupling of haloarenes with unactivated arenes has been developed in the presence of NaH and 1,10-phenanthroline. Various haloarenes bearing methyl, methoxy, halogen (fluoride, chloride, and bromide), cyano, trifluoromethyl, ester, and amide groups can be cross-coupled with unactivated arenes, or heteroarenes in this reaction.

Tetramethylammonium Fluoride Tetrahydrate-Mediated Transition Metal-Free Coupling of Aryl Iodides with Unactivated Arenes in Air.

Biaryls are important compounds with widespread applications in many fields. Tetramethylammonium fluoride tetrahydrate was found to promote the biaryl coupling of aryl iodides bearing electron-withdrawing substituents with unactivated arenes. The reaction takes place at temperatures between 100 and 150°C and can be applied to a wide range of aromatic and heteroaromatic rings, affording the products in moderate to high yields. The reaction does not require strong bases or expensive additives that are employed in the existing methods and can be conducted in air and moisture without any precautions.