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(sp(2))-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(sp(2))-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.

Closing the Cycle as It Begins: Synthesis of ortho-Iodobiaryls via Catellani Reaction / Botla, Vinayak; Fontana, Marco; Voronov, Aleksandr; Maggi, Raimondo; Motti, Elena; Maestri, Giovanni; Della Ca', Nicola. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - 62:18(2023), p. e202218928. [10.1002/anie.202218928]

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

Botla, Vinayak;Voronov, Aleksandr;Maggi, Raimondo;Motti, Elena;Maestri, Giovanni;Della Ca', Nicola
2023-01-01

Abstract

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(sp(2))-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(sp(2))-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.
2023
Closing the Cycle as It Begins: Synthesis of ortho-Iodobiaryls via Catellani Reaction / Botla, Vinayak; Fontana, Marco; Voronov, Aleksandr; Maggi, Raimondo; Motti, Elena; Maestri, Giovanni; Della Ca', Nicola. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - 62:18(2023), p. e202218928. [10.1002/anie.202218928]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2942631
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