Controlling Regioselectivity in Palladium‐Catalyzed C−H Activation/Aryl–Aryl Coupling of 4‐Phenylamino (2.2) paracyclophane

Abstract: Selective activation/functionalization of C−H bonds has emerged as an atom‐ and step‐economical process at the forefront of modern synthetic chemistry. This work reports palladium‐catalyzed exclusively para‐selective C−H activation/aryl–aryl bond formation with a preference over N‐arylation under the Buchwald–Hartwig amination reaction of 4‐phenylamino[2.2]paracyclophane. This innovative synthetic strategy allows a facile preparation of [2.2]paracyclophane derivatives featuring disparate para‐substitutions at C‐4 and C‐7 positions in a highly selective manner, gives access to a series of potential candidates for [2.2]paracyclophane‐derived new planar chiral ligands. The unprecedented behavior in reactivity and preferential selectivity of C−C coupling over C−N bond formation via C−H activation is unique to the [2.2]paracyclophane scaffold compared to the non‐cyclophane analogue under the same reaction conditions. Selective C−H activation/aryl–aryl bond formation and sequential C−N coupling product formation is evidenced unambiguously by X‐ray crystallography.

Object Details

• Location: Deutsche Nationalbibliothek Frankfurt am Main
• Extent: Online-Ressource
• Language: Englisch

References and Relationships

• Bibliographic citation: Controlling Regioselectivity in Palladium‐Catalyzed C−H Activation/Aryl–Aryl Coupling of 4‐Phenylamino (2.2) paracyclophane ; volume:26 ; number:61 ; year:2020 ; pages:13771-13775 ; extent:5 ; Chemistry - a European journal ; 26, Heft 61 (2020), 13771-13775 (gesamt 5)

Contributors, Places and Time

• Creator: Zippel, Christoph ; Spuling, Eduard ; Hassan, Zahid ; Polamo, Mika ; Nieger, Martin ; Bräse, Stefan

Further information

• DOI: 10.1002/chem.202003709
• URN: urn:nbn:de:101:1-2022060513484771858229
• Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
• Last update: 15.08.2025, 7:22 AM CEST