Palladium(II)‐Initiated Catellani‐Type Reactions

• Published in: Angewandte Chemie International Edition Vol. 58; no. 18; pp. 5832 - 5844
• Main Authors: Cheng, Hong‐Gang, Chen, Shuqing, Chen, Ruiming, Zhou, Qianghui
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 23.04.2019
• Edition: International ed. in English
• Subjects: Aromatic compounds; Catalysis; Catalysts; Catellani reaction; Chemical synthesis; cooperative catalysis; Coupling (molecular); C−H functionalization; Halides; norbornene; Palladium; palladium catalysis; Reaction mechanisms; Substrates; C−H functionalization; palladium catalysis; Catellani reaction; norbornene; cooperative catalysis
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201813491

The Catellani reaction is known as a powerful strategy for the expeditious synthesis of highly substituted arenes and benzo‐fused rings, which are usually difficult to access through traditional cross‐coupling strategies. It utilizes the synergistic interplay of palladium and norbornene catalysis to facilitate sequential ortho C−H functionalization and ipso termination of aryl halides in a single operation. In classical Catellani‐type reactions, aryl halides are mainly used as the substrates, and a Pd0 catalyst is required to initiate the reaction. Nevertheless, recent advances showcase that Catellani‐type reactions can also be initiated by a PdII catalyst with different starting materials instead of aryl halides via different reaction mechanisms and under different conditions. This emerging concept of PdII/norbornene cooperative catalysis has significantly advanced Catellani‐type reactions, thus enabling future developments of this field. In this Minireview, PdII‐initiated Catellani‐type reactions and their application in the synthesis of bioactive molecules are summarized. Cooperative solutions: Palladium(II)‐initiated norbornene (NBE)‐mediated cooperative catalysis has enabled significant developments of the Catellani reaction. These advances and their application in the synthesis of bioactive molecules are summarized in this Minireview.