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

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

doi:10.1002/chem.202003709

Cited by 8 publications

(5 citation statements)

References 55 publications

(21 reference statements)

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“…[25] Anilines derived from pCp have finally been described to undergo C─H activation reactions at their para position capable of generating new carbon-carbon bonds (Scheme 5b). [26] As described hereabove, most of the strategies reported in the literature up to now enable the preparation of useful synthetic intermediates derived from pCp bearing various functional groups at their ortho and para positions. On the contrary, the development of new reactions leading to the selective functionalization of mono-substituted compounds at their meta position still appears difficult to achieve.…”

Section: Selective Decoration Of Only One Deckmentioning

confidence: 99%

[2.2]Paracyclophanes: From Selective Functionalization to Optical Properties

Wu,

Felder,

Brom

et al. 2024

Advanced Optical Materials

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Since their discovery, [2.2]paracyclophane (pCp) and its derivatives have fascinated the scientific community due to their original molecular architecture and unusual electronic behavior. Over the years, significant efforts have been devoted to the development of substituted pCps for a variety of applications in different fields, ranging from organic synthesis and asymmetric catalysis to polymer chemistry and material science. This review describes a series of useful approaches that allow chemists to selectively decorate pCps, control the planar chirality that these molecules can display as soon as they are functionalized, and tune their photophysical behaviors. For each of these aspects of paracyclophane chemistry, selected examples of major advances are presented, and possible directions for future research are outlined. The application of pCp as central core for the development of uncommon 3D luminophores is finally highlighted. Emphasis is placed on the potential use of planar chiral luminescent paracyclophanes as antennas or ligands for the design of multifunctional lanthanide complexes, a quite underdeveloped but highly promising area for future research endeavors.

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Section: Selective Decoration Of Only One Deckmentioning

confidence: 99%

[2.2]Paracyclophanes: From Selective Functionalization to Optical Properties

Wu,

Felder,

Brom

et al. 2024

Advanced Optical Materials

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“…To this date, no directing groups are known that would steer catalytic arylations selectively into the aniline para position. Only certain specialized C−C couplings, such as benzidine rearrangements [20] or oxidative dimerizations, [21] produce para ‐arylated aniline derivatives [22] . The current selectivity record in aniline C−H arylations is held by Gaunt et al., who achieved high para ‐selectivity in a copper‐catalyzed coupling of doubly benzylated anilines with highly reactive diaryliodonium salts, however along with ortho / para‐ diarylated byproducts [23] .…”

Section: Figurementioning

confidence: 99%

Palladium‐Catalyzed para‐C−H Arylation of Anilines with Aromatic Halides

et al. 2022

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Controlling regioselectivity in CÀ H functionalizations is a key challenge in chemical method development. In arenes, functionalizations are most difficult to direct towards the CÀ H group furthest away from a substituent, in its para position. We herein demonstrate how the para-CÀ H arylation of anilines with nonactivated aryl halides, elusive to date, is achieved by a base-assisted "metalla-tautomerism" approach. A proton is abstracted from the aniline substrate and replaced by an arylpalladium species, generated from the aryl halide coupling partner. In this step, the palladium is directed away from the N-to the tautomeric para-CÀ H position by a large phosphine ligand combined with a triphenylmethyl shielding group. The triphenylmethyl group is easily installed and removed, and can be recycled.

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“…Bis heute sind keine dirigierenden‐Gruppen bekannt, die katalytische Arylierungen selektiv in die para ‐Position des Anilins lenken würden. Nur bestimmte spezialisierte C−C‐Kupplungen, wie Benzidin‐Umlagerungen [20] oder oxidative Dimerisierungen, [21] führen zu para ‐arylierten Anilinderivaten [22] . Der derzeitige Selektivitätsrekord bei Anilin‐C−H‐Arylierungen wird von Gaunt et al.…”

Section: Figureunclassified

“…Nur bestimmte spezialisierte CÀ C-Kupplungen, wie Benzidin-Umlagerungen [20] oder oxidative Dimerisierungen, [21] führen zu paraarylierten Anilinderivaten. [22] Der derzeitige Selektivitätsrekord bei Anilin-CÀ H-Arylierungen wird von Gaunt et al gehalten, die bei einer kupferkatalysierten Kupplung von doppelt benzylierten Anilinen mit hochreaktiven Diaryliodoniumsalzen eine hohe para-Selektivität erzielten, allerdings mit ortho-/para-diarylierten Nebenprodukten. [23] Dieser Reaktionstyp wurde von Kita für Anisolderivate implementiert.…”

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Palladium‐katalysierte para‐C−H Arylierung von Anilinen mit aromatischen Halogeniden

et al. 2022

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Die Kontrolle der Regioselektivität bei CÀ H-Funktionalisierungen ist eine zentrale Herausforderung bei der chemischen Methodenentwicklung. Bei Arenen ist es am schwierigsten, Funktionalisierungen auf die CÀ H-Gruppe zu richten, die am weitesten von einem Substituenten entfernt ist, nämlich in para-Position. Wir zeigen hier, wie die para-CÀ H-Arylierung von Anilinen mit nicht aktivierten Arylhalogeniden, die bisher schwer zu erreichen war, durch einen basenvermittelten "Metalla-Tautomerie"-Ansatz erreicht wird. Ein Proton wird aus dem Anilin-Substrat abstrahiert und durch eine Arylpalladium-Spezies ersetzt, die aus dem Arylhalogenid-Kupplungspartner erzeugt wird. In diesem Schritt wird das Palladium durch einen großen Phosphanliganden in Kombination mit einer Triphenylmethyl-Schutzgruppe von der N-zur tautomeren para-CÀ H-Position gelenkt. Die Triphenylmethylgruppe lässt sich leicht anbringen und entfernen und kann recycelt werden.

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

Abstract: Scheme2.Pd-catalyzed para-selective CÀHa ctivation/aryl-arylc oupling underc lassical Buchwald-Hartwig-amination of N-phenylamino[2.2]paracyclophane (0.5 mmol, 0.17 m): PhBr (0.6 mmol), Pd 2 dba 3 (5.0 mol %), SPhos (5.0 mol %), KOtBu (1.0 mmol), PhMe,1 20 8C, 48 h.

Cited by 8 publications

References 55 publications

[2.2]Paracyclophanes: From Selective Functionalization to Optical Properties

[2.2]Paracyclophanes: From Selective Functionalization to Optical Properties

Palladium‐Catalyzed para‐C−H Arylation of Anilines with Aromatic Halides

Palladium‐katalysierte para‐C−H Arylierung von Anilinen mit aromatischen Halogeniden

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