Tunable Rh(III)-Catalyzed C(sp²)–H Bond Functionalization of Aryl Imidates with Cyclic 1,3-Diones: Strategic Use of Directing Groups

A tunable Rh(III)-catalyzed C(sp²)-H bond functionalization of aryl imidates with cyclic 1,3-diones was developed. With suitable and straightforward reaction condition adjustments, the C-H bond functionalization of diverse aryl imidates with cyclic 1,3-diones occurred smoothly and precisely at room temperature. Accompanied by different directing group transformations, a series of corresponding aryl nitriles, hydrophenanthridin-1(2<i>H</i>)-ones, spiro isoindoles, or hydrophenanthridine-1,6(2<i>H</i>,5<i>H</i>)-diones were synthesized in good yields to provide a rational directing group utilization strategy for the Rh(III)-catalyzed C(sp²)-H bond activation. Control experiments and primary mechanistic studies revealed that solvent effects and functional group electronic effects might influence the reaction's selectivity.