Closing the Cycle as It Begins: Synthesis of <i>ortho</i>‐Iodobiaryls via Catellani Reaction
Vinayak Botla, Marco Fontana, Aleksandr Voronov, Raimondo Maggi, Elena Motti, Giovanni Maestri, Nicola Della Ca’
Abstract
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.