Meta‐Selective C−H Arylation of Fluoroarenes and Simple Arenes. Issue 33 (9th July 2020)

• Record Type: Journal Article
• Authors: Liu, Luo‐Yan; Qiao, Jennifer X.; Yeung, Kap‐Sun; Ewing, William R.; Yu, Jin‐Quan
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 33(2020)
• Page Start: 13831
• Page End: 13835
• Publication Date: 2020-07-09
• Subjects: arylation -- homogeneous catalysis -- C−H activation -- fluoroarenes -- palladium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202002865
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Fluorine is known to promote ortho ‐C−H metalation. Based upon this reactivity, we employed an activated norbornene that traps the ortho ‐palladation intermediate and is then relayed to the meta position, leading to meta ‐selective C−H arylation of fluoroarenes. Deuterium experiment suggests that this meta ‐arylation is initiated by ortho C−H activation and the catalytic cycle is terminated by C‐2 protonation. A dual‐ligand system is crucial for the observed high reactivity and site selectivity. Applying this approach to simple benzene or other arenes also affords arylation products with good yield and site selectivity. Abstract : meta ‐Selective C−H arylation : An activated norbornene traps the ortho ‐palladation intermediate in the ortho ‐C−H metalation of fluoroarenes and is then relayed to the meta position, leading to meta ‐selective C−H arylation. A dual‐ligand system is crucial for the observed high reactivity and selectivity. Applying this approach to simple benzene or other arenes also affords arylation products with good yields and site selectivity.