Catellani Reaction: An Enabling Technology for Vicinal Functionalization of Aryl Halides by Palladium(0)/Norbornene Cooperative Catalysis

Abstract The Catellani reaction, originally discovered by Catellani in 1997, and further developed by Catellani, Lautens and others, has emerged as a powerful strategy for the synthesis of polysubstituted arenes, which would be difficult to access via traditional methods. In this process, both ortho ‐ and ipso ‐positions of aryl halides could be functionalized simultaneously with different electrophiles and terminating agents under the cooperative catalysis of palladium and norbornene (NBE). This review focuses on the significant progress of such transformations, and the section of typical Catellani reactions is divided into five parts according to the functionalization mode of ortho‐ C—H bond: alkylation, arylation, amination, acylation or thiolation.