Extended Data Fig. 2: Mechanistic investigations.
From: β-C−H bond functionalization of ketones and esters by cationic Pd complexes
A, Deuterium incorporation experiments condition: 1a (0.1 mmol), Pd(OAc)2 (10 mol%), ArI (2.0 equiv.), ligand L1 (10 mol%), Ag2CO3 (2.0 equiv.), DOTf (1.5 equiv.), HFIP-OD (2.0 ml), 80 °C, 12 h. B, Parallel kinetic isotopic effect (KIE) studies condition: 1f or [D3]1f (0.1 mmol), Pd(OAc)2 (10 mol%), ArI (2.0 equiv.), ligand L1 (10 mol%), Ag2CO3 (2.0 equiv.), Et2O·HBF4 (1.5 equiv.), HFIP (2.0 ml), 80 °C, 3-75 min. C, Palladium charge and ligand effects on the C(sp3)−H cleavage step. i) Effect of cationic Pd on substrate coordination. ii) Ligand effect on C(sp3)−H cleavage transition state (TS). All quasi-harmonic free energies are reported at 353 K relative to separated reactants. D, C(sp3)−H hydroxylation with water as a solo hydroxyl source. Reaction conditions: 1s (0.1 mmol), PdCl2(PPh3)2 (10 mol%), ligand L3 (10 mol%), Selectfluor (2.5 equiv.), Ag2CO3 (1.5 equiv.), Et2O·HBF4 (1.5 equiv.), water (2.0 equiv.), HFIP (2.0 ml), 50 °C, 48 h, under N2.
