TY - JOUR

T1 - Bioinspired Non-Heme Mn Catalysts for Regio- and Stereoselective Oxyfunctionalizations with H2O2

AU - Ottenbacher, Roman V

AU - Bryliakova, Anna A

AU - Kurganskii, Vladimir I

AU - Prikhodchenko, Petr V

AU - Medvedev, Alexander G

AU - Bryliakov, Konstantin Petrovich

N1 - Acknowledgments RVO, AAB, VIK, KPB thank the Russian Science Foundation (grant 20-13-00032) for financial support. The authors thank Dr. O. Y. Lyakin for providing the ligand for the synthesis of complex 17. AAB thanks the access to the supercomputer facilities of the Computing Centre of Novosibirsk State University. © 2023 Wiley-VCH GmbH.

PY - 2023/11/24

Y1 - 2023/11/24

N2 - 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).

AB - 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).

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85174191155&origin=inward&txGid=b958cf734ca488f5ed375422255ec59f

UR - https://www.mendeley.com/catalogue/d2b65bd7-a4af-3927-87ea-fb10b5dbed2a/

U2 - 10.1002/chem.202302772

DO - 10.1002/chem.202302772

M3 - Review article

C2 - 37642264

VL - 29

SP - 1

EP - 16

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 66

M1 - e202302772

ER -