Isatoic anhydride as a masked directing group and internal oxidant for Rh(III)-catalyzed decarbonylative annulation through C-H activation: insights from DFT calculations.

Density functional theory calculations uncovered a new mechanism for the rhodium-catalyzed decarbonylative annulation of isatoic anhydride with alkynes, in which the acyloxy group formed from the N-H deprotonation and C-O bond cleavage of isatoic anhydride acts as the directing group to assist the C-H activation. From the generated five-membered rhodacycle intermediate, the final aminoisocoumarin product could be formed by subsequent steps of alkyne insertion, reductive elimination, decarbonylation, and protonation. The isocyanate moiety contained in the annulation intermediate was uncovered as a novel internal oxidant for the reaction, which oxidizes the Rh(I) to Rh(III) by decarbonylation.