An Rh­(III)-catalyzed 1,1-cyclization of N-methoxy benzamides with maleimides providing isoindolinone spirosuccinimides through N–H/C–H/N–O bond activation is described. The detailed mechanistic investigation including isolation of key metalacycle intermediate, deuterium labeling studies, and DFT calculations were performed. The computational study reveals that the AcOH that formed in the reaction medium plays a key role in the N–OMe bond cleavage and the oxidation of Rh­(I) to Rh­(III).

The first ever attempt at reacting hypervalent iodonium ylides with readily available N-methoxybenzamides by using a Rh(iii)-catalyst has been well explored.

1H-Isoindoles and 2H-isoindoles are synthesized via a ruthenium-catalyzed oxidant-free cyclization of benzimidates with alkenes at room temperature with the liberation of H. Later, 1H-isoindoles were converted into nitrogen-containing heterocycles. The proposed reaction mechanism was strongly supported by experimental evidence and DFT calculations.

A rhodium(III)-catalyzed ortho-alkenylation of substituted anilides with maleimides providing 3-arylated maleimides in good to excellent yields is described. In the reaction, a minor amount of Michael-type addition product, 3-arylated succinimides, was also observed. Later, 3-arylated succinimides was converted into 3-arylated maleimides in the presence of diisopropyl azodicarboxylate and K 2 CO 3 . Generally, a Michael-type 3arylated succinimides was observed in the reaction of maleimides with substituted aromatics via C-H bond activation. In the present reaction, unusually, a Heck-type alkenylated product was observed in the major amount. A possible reaction mechanism was proposed and supported by the deuterium labelling studies and computational experiments. The mechanistic investigation and DFT calculations revealed that the time interval for the regeneration of Rh(I) to Rh(III) could be the factor for the observation of a minor ortho alkylated aromatics which was formed via a redox neutral Rh(III) version.[a] Dr.