Bioinspired Non‐Heme Mn Catalysts for Regio‐ and Stereoselective Oxyfunctionalizations with H2O2

In recent years, metalloenzymes‐mediated highly selective oxidations of organic substrates under mild conditions have been inspiration for developing synthetic bioinspired catalyst systems, capable of conducting such processes in the laboratory (and, in the future, in industry), relying on easy‐to‐handle and environmentally benign oxidants such as H2O2. To date, non‐heme manganese complexes with chiral bis‐amino‐bis‐pyridylmethyl and structurally related ligands are considered as possessing the highest synthetic potential, having demonstrated the ability to mediate a variety of chemo‐ and stereoselective oxidative transformations, such as epoxidations, C(sp3)‐H hydroxylations and ketonizations, oxidative desymmetrizations, kinetic resolutions, etc. Furthermore, in the past few years non‐heme Mn based catalysts have become the major platform for studies focused on getting insight into the molecular mechanisms of oxidant activation and (stereo)selective oxygen transfer, testing non‐traditional hydroperoxide oxidants, engineering catalytic sites with enzyme‐like substrate recognition‐based selectivity, exploration of catalytic regioselectivity trends in the oxidation of biologically active substrates of natural origin. This contribution summarizes the progress in manganese catalyzed C‐H oxygenative transformations of organic substrates, achieved essentially in the past 5 years (late 2018–2023). Mn catalyzed C‐H activation: In recent years, Mn based catalysts have been at the forefront of direct oxidative functionalization of organic compounds with hydrogen peroxide. This contribution surveys the progress in this emerging area, achieved in the past five years, with focus on the possibilities for tuning the chemo‐, regio‐, and stereoselectivity of these catalyst systems.