Installing Axial Chirality by Atroposelective C(sp ³ )–H Bond Oxidation

as oxidant, enabling compatibility with configurationally labile substrates and tolerance toward a wide variety of functional groups that are typically sensitive in organometallic catalysis. The devoid of directing groups on the substrate core allows access to axially chiral biaryls (42 examples) decorated with a plethora of functionalities in high yields (up to 88%) and outstanding enantioselectivity ratios (up to >99% ee). Furthermore, the exquisite site- and enantioselective C-H oxidation activity of the catalysts enables subsequent site- and chemoselective oxidation of the second methyl group, offering a novel and versatile platform for elaboration of the biaryl core. Overall, the catalysts' activity enables recognition of methyl groups as functional groups for synthetic manipulations, showcasing the strategic use of C-H bond functionalization reactions as a powerful approach for stereoselective synthesis.