Synthesis of Heptagon‐Containing Polyarenes by Catalytic C−H Activation

Nanocarbons incorporating non‐hexagonal aromatic rings ‐ such as five‐, seven‐, and eight‐membered rings ‐ have various intriguing physical properties such as curved structures, unique one‐dimensional packing, and promising magnetic, optical, and conductivity properties. Herein, we report an efficie...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-12, Vol.62 (51), p.e202311770-n/a
Main Authors: Yamada, Keigo E., Stepek, Iain A., Matsuoka, Wataru, Ito, Hideto, Itami, Kenichiro
Format: Article
Language:English
Subjects:
Aromatic compounds
Chemical synthesis
Magnetic properties
Nanocarbons
Optical properties
Palladium
Physical properties
Polycyclic Aromatic Hydrocarbon
Rhodium
Synthetic Methods
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Summary:Nanocarbons incorporating non‐hexagonal aromatic rings ‐ such as five‐, seven‐, and eight‐membered rings ‐ have various intriguing physical properties such as curved structures, unique one‐dimensional packing, and promising magnetic, optical, and conductivity properties. Herein, we report an efficient synthetic approach to polycyclic aromatics containing seven‐membered rings via a palladium‐catalyzed intramolecular Ar−H/Ar−Br coupling. In addition to all‐hydrocarbon scaffolds, heteroatom‐embedded heptagon‐containing polyarenes can be efficiently constructed with this method. Rhodium‐ and palladium‐catalyzed sequential six‐ and seven‐membered ring formations also afford complex heptagon‐containing molecular nanocarbons from readily available arylacetylenes and biphenyl boronic acids. Detailed mechanistic analysis by DFT calculations showed the feasibility of seven‐membered ring formation by a concerted metalation‐deprotonation mechanism. This reaction can serve as a template for the synthesis of a wide range of seven‐membered ring‐containing molecular nanocarbons. Herein, we report an efficient synthetic method, involving a Pd‐catalyzed intramolecular coupling, for polycyclic aromatic compounds containing seven‐membered rings. A variety of heptagon‐containing molecular nanocarbons were synthesized. In addition, a one‐pot synthetic method comprising Rh‐catalyzed annulation and Pd‐catalyzed cyclization was developed. Furthermore, it was possible to construct two seven‐membered rings simultaneously.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202311770