“…Among the numerous C-H activation catalysts, Cp*Rh(III)/Ir(III) complexes have stood out as competent catalysts for directing group-assisted direct C−H functionalization with high catalytic activity, selectivity, and functional group tolerance [32][33][34][35][36][37][38][39]. So far, the Rh(III)-catalyzed C−H amination proceeded via chelation-assisted strategies include the following categories on the basis of the distinct mechanism: (1) the nitrene insertion using nitrene precursors such as organic azides, dioxazolones, anthranils, and TsNH2/PhI(OAc)2 (Scheme 1(a)) [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48]61,68,69], (2) SN-type amination using an electrophilic aminating reagent (Scheme 1b) [49][50][51][52][53][54][55][56][57][58][59][60] and (3) the oxidative amination using a nucleophilic aminating re-agent (Scheme 1(c)) [70]. Although amination has been realized under redox-neutral conditions using nitrenoid reagents [40][41][42]…”