Cobalt/Rhodium-Catalyzed Diversified Amidation of Benzocyclobutenols via C-C Cleavage under Catalyst and Condition Control

Cobalt(III)and rhodium(III)-catalyzed regio- and chemoselectiveamidation of benzocyclobutenols has been realized using dioxazoloneas the amidating reagent to afford three classes of C-N-coupledproducts via & beta;-carbon elimination of the benzocyclobutenol.The Co(III)-catalyzed coupling initially afforded an isolable o-(N-acylamino)arylmethyl ketone, whichcould further cyclize to the corresponding indole derivatives undercondition control. In contrast, efficient stepwise diamidation hasbeen achieved under Rh(III) catalyst control. The chemoselectivitiesare jointly controlled by the catalyst and reactions conditions.

Automated summary

Regio- and chemoselective amidation of benzocyclobutenols has been achieved using dioxazolone as the amidating reagent and cobalt(III) or rhodium(III) catalysts. The cobalt(III)-catalyzed coupling first forms an isolable o-(N-acylamino)arylmethyl ketone, which can further cyclize to indole derivatives. In contrast, efficient stepwise diamidation is achieved under rhodium(III) catalyst control. The chemoselectivity is controlled by the catalyst and reaction conditions.