Abstract

The regioselective C−H functionalization of arenes is an ideal method for preparing substituted aromatic compounds, which are ubiquitous scaffolds in natural products, pharmaceuticals, and advanced materials. Palladium(0)-catalyzed, norbornene-mediated C−H functionalization—now known as the Catellani reaction—is a particularly efficient and modular means to access densely substituted aromatic compounds. Inspired by the Catellani reaction, many palladium(II)-catalyzed variants have been developed, further expanding the synthetic utility of this chemistry.

The Catellani reaction functionalizes both the ortho and ipso positions of the starting haloarene. Products are obtained with excellent regioselectivity, and enantioenriched norbornene derivatives may be used to render The Reaction">the reaction enantioselective. This method enables ortho-alkylation, -arylation, and -amination of various arene substrates, and can be combined with other palladium-catalyzed processes. The mechanism, development, and applications of Catellani-type reactions are discussed in this chapter.