Mechanistic studies of Cp*Ir(iii)/Cp*Rh(iii)-catalyzed branch-selective allylic C–H amidation: why is Cp*Ir(iii) superior to Cp*Rh(iii)?

Density functional theory calculations have revealed the mechanism and origins of the reactivity and regioselectivity of the Cp*Ir(iii)/Cp*Rh(iii)-catalyzed allylic C-H amidation of alkenes and dioxazolones. Generally, the catalytic cycle consists of alkene coordination, C(sp3)-H activation, dioxazolone oxidative addition, reductive elimination and proto-demetallation to give the final amidation product. The C-H activation is found to be the...