Mechanism and selectivity on IrIII/RhIII-catalyzed coupling of terminal alkenes and dioxazolones: A DFT study

• The mechanism and Selectivity on amidation of terminal alkenes with the nitrene precursors was explored with the aid of DFT calculations. Additionally, influence of the catalyst Ir(III) vs Rh(III) on the selectivity of above reactions was also elucidated. The Cp*IrIII-catalyzed coupling of terminal alkenes with dioxazolones to achieve C H amidation was studied theoretically with the aid of the density functional calculations. Employing the Ir=nitrenoid intermediate species involved in the reaction mechanism, the Ir N R bonding nature was analyzed based on LUMO/HOMO interactions. Especially, the branch-selectivity with Cp*Ir(III) as the catalyst, the influence of Ir(III) vs Rh(III) on branch/linear selectivity, and the impossibility of aziridination were elucidated. This work provided further understanding and beneficial information for designing novel related selective reactions.