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

Zippel, Christoph 1; Spuling, Eduard 1; Hassan, Zahid 1; Polamo, Mika; Nieger, Martin; Bräse, Stefan 1
1 Institut für Organische Chemie (IOC), Karlsruher Institut für Technologie (KIT)


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.

Verlagsausgabe §
DOI: 10.5445/IR/1000125595
Veröffentlicht am 03.11.2020
DOI: 10.1002/chem.202003709
Zitationen: 3
Web of Science
Zitationen: 3
Zitationen: 4
Cover der Publikation
Zugehörige Institution(en) am KIT 3D Matter Made to Order (3DMM2O)
Institut für Biologische und Chemische Systeme (IBCS)
Institut für Organische Chemie (IOC)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 02.11.2020
Sprache Englisch
Identifikator ISSN: 0947-6539, 1521-3765
KITopen-ID: 1000125595
HGF-Programm 47.01.01 (POF III, LK 01) Biol.Netzwerke u.Synth.Regulat. ITG+ITC
Erschienen in Chemistry - a European journal
Verlag John Wiley and Sons
Band 26
Heft 61
Seiten 13771-13775
Vorab online veröffentlicht am 15.08.2020
Nachgewiesen in Web of Science
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