Closing the Cycle as It Begins: Synthesis of ortho‐Iodobiaryls via Catellani Reaction

Despite the advances in the field of carbon‐halogen bond formation, the straightforward catalytic access to selectively functionalized iodoaryls remains a challenge. Here, we report a one‐pot synthesis of ortho‐iodobiaryls from aryl iodides and bromides by palladium/norbornene catalysis. This new ex...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-04, Vol.62 (18), p.e202218928-n/a
Main Authors: Botla, Vinayak, Fontana, Marco, Voronov, Aleksandr, Maggi, Raimondo, Motti, Elena, Maestri, Giovanni, Della Ca', Nicola
Format: Article
Language:English
Subjects:
Aromatic compounds
Aryl Iodides
Bromides
Catalysis
Catellani Reactions
C−H Arylation
Halides
Iodides
Palladium
Reductive Elimination
Synthesis
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Summary:Despite the advances in the field of carbon‐halogen bond formation, the straightforward catalytic access to selectively functionalized iodoaryls remains a challenge. Here, we report a one‐pot synthesis of ortho‐iodobiaryls from aryl iodides and bromides by palladium/norbornene catalysis. This new example of Catellani reaction features the initial cleavage of a C(sp2)−I bond, followed by the key formation of a palladacycle through ortho C−H activation, the oxidative addition of an aryl bromide and the ultimate restoration of the C(sp2)−I bond. A large variety of valuable o‐iodobiaryls has been synthesized in satisfactory to good yields and their derivatization have been described too. Beyond the synthetic utility of this transformation, a DFT study provides insights on the mechanism of the key reductive elimination step, which is driven by an original transmetallation between palladium(II)‐halides complexes. A new strategy based on the Catellani reactions has enabled the one‐pot synthesis of ortho‐iodobiaryls starting from aryl iodides and bromides. Beyond the synthetic utility of this transformation (32 examples and 6 subsequent derivatizations), a DFT study provides insights on the mechanism of the reductive elimination step, which is driven by an original transmetallation between palladium(II)‐halide complexes.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202218928