Palladium-Catalyzed Site-Selective [3+2] Annulation via Benzylic and meta C-H Bond Activation

The palladium-catalyzed [3+2] annulation of aromatic amides with maleimides via the activation of ortho benzylic C-H and meta C-H bonds is reported. Carboxamide and anilide type substrates that contain a 2-methylthiophenyl group both participate in this [3+2] annulation, indicating that the presence of a 2-methylthiophenyl directing group is a key for the success of the reaction. The first C-H bond activation at the benzylic C-H bond is followed by a second C-H bond activation at the meta C-H bond to give five-membered cyclic products. The cleavage of these C-H bonds is irreversible.

Automated summary

The palladium-catalyzed [3+2] annulation of aromatic amides with maleimides via the activation of ortho benzylic C-H and meta C-H bonds is reported, with a key role played by the presence of a 2-methylthiophenyl directing group for the success of the reaction. The irreversible cleavage of these C-H bonds leads to the formation of five-membered cyclic products.