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

Bi S.;* Chu, Y.; Meng R.; Wu, X.; Jiang, Y.-Y.; Liu, Y.; Ling, B.  Mol. Catal. 2021, 510, 111679. Download Link

Abstract: 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.