“…Further, the currently available general approaches for modulating the regioselectivity of C(sp 3 )–H oxidation of steroids and terpenoids (e.g., by changing the catalysts’ sterics and chirality, and the central atom, cocatalytic additives, solvent, or supramolecular recognition) should be tested and adapted for a broader scope of potentially interesting classes of complex substrates of natural origin, including alkaloids, peptides, amides, etc., as well as synthetic compounds of interest for drug discovery. In addition, while at present we have learned how to oxidize aliphatic C(sp 3 )–H groups of molecules that also contain aromatic C(sp 2 )–H groups with sufficient chemo- and stereoselectivity, ,, the opposite is not the case (yet recent contributions inspire some optimism − ). The “alternative rebound mechanism” introduces another dimension into catalytic C–H functionalization: while the C–H activation regio- and stereoselectivity is governed by the architecture of the chiral ligand, the nature of the novel C–X group depends on the nature of the cocatalytic additive.…”