Biaryl Synthesis via Electrooxidative Transition Metal Catalyzed C−H Activation

The use of electricity as an inexpensive and waste-free oxidant opens up new opportunities for the development of sustainable C–H functionalization reactions. Herein we summarize recent advances in the synthesis of biaryls through electrooxidative processes involving transition metal catalyzed ortho-directed C−H activation. A particular focus is set on electrooxidative C−H/C−M couplings and dehydrogenative couplings.

Synthesis of Xylyl-Linked Bis-Benzimidazolium Salts and Their Application in the Palladium-Catalyzed Suzuki–Miyaura Cross-Coupling Reaction of Aryl Chlorides

A new series of xylyl-linked bis-benzimidazolium salts were efficiently prepared using a simple preparation method from bis-benzimidazolium precursors featuring highly tunable linkers and wingtips. A highly efficient Suzuki–Miyaura cross-coupling reaction of aryl chlorides within the range of 0.5–2.0 mol% Pd-catalyst loading was observed. Also, di-ortho-substituted biaryl synthesis was achieved.

Biaryl Construction Based on Nickel-Catalyzed C–O Bond Activation

Nickel-catalyzed carbon–oxygen bond activation is one of the most powerful strategies for the direct construction of various biaryl compounds. Under nickel catalysis, efficiently produced and naturally abundant arenol-based electrophiles can be activated and coupled with different aryl nucleophiles, including nucleophiles containing magnesium, zinc, boron, etc., to produce biaryl structural units. This Account summarizes recent progress on biaryl synthesis via nickel-catalyzed C–O bond activation.1 Introduction2 Coupling of Arenols and Arenol Derivatives with Aryl Magnesium Reagents3 Coupling of Arenols and Arenol Derivatives with Aryl Zinc Reagents4 Coupling of Arenols and Arenol Derivatives with Aryl Boron Reagents5 Others6 Conclusion

Arylation of aryllithiums with S-arylphenothiazinium ions for biaryl synthesis

Aryllithiums were arylated with S-arylphenothiazinium ions through selective ligand coupling of intermediary sulfuranes. Various unsymmetrical biaryls were obtained without transition-metal catalysis.