Asymmetric Autoamplification in the Oxidative Kinetic Resolution of Secondary Benzylic Alcohols Catalyzed by Manganese Complexes

  title={Asymmetric Autoamplification in the Oxidative Kinetic Resolution of Secondary Benzylic Alcohols Catalyzed by Manganese Complexes},
  author={Evgenii P. Talsi and Denis G. Samsonenko and Konstantin P. Bryliakov},
Herein, chiral Mn–aminopyridine complexes have been shown to catalyze the oxidation of alkylarenes to enantiomerically enriched 1‐arylalkanols with hydrogen peroxide. The observed enantiomeric excess values result from the direct enantioselective benzylic C−H hydroxylation, accompanied by stereoconvergent oxidative kinetic resolution of the resulting alcohol. Testing several (S,S)‐bipyrrolidine derived Mn complexes has revealed a novel catalyst (6) that exhibits the best kinetic resolution in… 
Highly Enantioselective Oxidation of Spirocyclic Hydrocarbons by Bioinspired Manganese Catalysts and Hydrogen Peroxide
Bioinspired manganese complexes have emerged as attractive catalysts for a number of selective oxidation reactions over the past several decades. In the present study, we report the enantioselective
Chiral Manganese Aminopyridine Complexes: the Versatile Catalysts of Chemo- and Stereoselective Oxidations with H2 O2.
This personal account summarizes the progress of manganese(II) complexes with N-donor tetradentate aminopyridine ligands with regard to ligands design, structure-reactivity correlations, evaluation of the substrate scope, as well as mechanistic studies, shedding light on the nature of active sites and the mechanisms of selective oxygenations.
Mechanistic Insights into the Enantioselective Epoxidation of Olefins by Bioinspired Manganese Complexes: Role of Carboxylic Acid and Nature of Active Oxidant
Bioinspired manganese and iron complexes bearing nonporphyrinic tetradentate N4 ligands are highly efficient catalysts in asymmetric oxidation reactions by hydrogen peroxide (H2O2), in which
Autoamplification‐Enhanced Oxidative Kinetic Resolution of sec‐Alcohols and Alkyl Mandelates, and its Kinetic Model
In this contribution, the new dynamic nonlinear effect in asymmetric catalysis is discussed, manifesting itself in the oxidative kinetic resolution (OKR) of racemic secondary benzylic alcohols and
Palladium aminopyridine complexes catalyzed selective benzylic C-H oxidations with peracetic acid.
Preliminary mechanistic data provide evidence in favor of metal complex-mediated rate-limiting benzylic C-H bond cleavage by an electron-deficient oxidant.
Enantioselective Benzylic Hydroxylation of Arylalkanes with H2O2 in Fluorinated Alcohols in the Presence of Chiral Mn Aminopyridine Complexes
A series of chiral bioinspired Mn‐aminopyridine complexes of the type [L*MnII(OTf)2] (where L* is 2,2′‐bipyrrolidine derived ligand, bearing trifluoroalkoxy and alkyl substituents) have been tested
Catalytic Asymmetric Oxygenations with the Environmentally Benign Oxidants H2O2 and O2.
An overview of catalyst systems capable of conducting asymmetric oxygenative transformations of organic molecules and, in line with the major trend to sustainability, relying on green oxidants H2O2 and O2 as the ultimate oxygen source is given.
Oxidative functionalization of C–H compounds induced by the extremely efficient osmium catalysts (a review)
Osmium derivatives are not as popular among catalytic chemists as the compounds of iron (an analog of osmium), copper, or manganese. Although osmium is expensive, poisonous and volatile, it finds
Enantioselective aliphatic C-H bond oxidation catalyzed by bioinspired complexes.
The present work reviews the current status of field, analyzing the difficulties of the reaction, discussing principles of catalyst design, and critically highlighting the limitations of the current state-of-the-art methodologies.
Catalytic Asymmetric C–H Oxidation with H2O2 and O2
  • K. Bryliakov
  • Chemistry, Biology
    Green Chemistry and Sustainable Technology
  • 2019
This chapter surveys the existing catalyst systems, either organocatalytic or metal-based, for the chemo- and stereoselective oxidation of C–H groups with the environmentally benign oxidants H2O2 and


Highly Enantioselective Bioinspired Epoxidation of Electron-Deficient Olefins with H2O2 on Aminopyridine Mn Catalysts
The asymmetric epoxidation of various electron-deficient olefins with H2O2 in the presence of a novel family of chiral bioinspired bipyrrolidine-derived aminopyridine manganese(II) complexes
Asymmetric Epoxidations with H2O2 on Fe and Mn Aminopyridine Catalysts: Probing the Nature of Active Species by Combined Electron Paramagnetic Resonance and Enantioselectivity Study
Chiral bipyrrolidine based iron and manganese complexes [((S,S)-pdp)MII(OTf)2] catalyze the asymmetric epoxidation of various olefins with H2O2 in the presence of carboxylic acid additives with high
The palladium-catalyzed oxidative kinetic resolution of secondary alcohols with molecular oxygen.
This work presents the development of a catalytic oxidative kinetic resolution of secondary alcohols that uses molecular oxygen as the terminal oxidant (see Scheme 1).
Selective Catalytic Oxidation of CH Bonds with Molecular Oxygen
Although catalytic reductions, cross‐couplings, metathesis, and oxidation of CC double bonds are well established, the corresponding catalytic hydroxylations of CH bonds in alkanes, arenes, or
Enantioselective Epoxidations of Olefins with Various Oxidants on Bioinspired Mn Complexes: Evidence for Different Mechanisms and Chiral Additive Amplification
It has been demonstrated that chiral manganese aminopyridine complexes [LMnII(OTf)2] are able to epoxidize olefins with excellent enantioselectivities (up to 99% ee, several examples) with various
Highly Enantioselective Oxidation of Nonactivated Aliphatic C–H Bonds with Hydrogen Peroxide Catalyzed by Manganese Complexes
The principles of catalyst design disclosed in this work constitute a unique platform for further development of stereoselective C–H oxidation reactions and represent the first example of nonenzymatic highly enantioselectives oxidation of nonactivated methylenic sites.
Direct Selective Oxidative Functionalization of C–H Bonds with H2O2: Mn-Aminopyridine Complexes Challenge the Dominance of Non-Heme Fe Catalysts
In this mini-review, recent catalytic and mechanistic data on the selective C-H oxygenations with H₂O₁ in the presence of manganese complexes are overviewed.
A Mononuclear Manganese Complex of a Tetradentate Nitrogen Ligand – Synthesis, Characterizations, and Application in the Asymmetric Epoxidation of Olefins
A new chiral manganese complex (C1) bearing a tetradentate nitrogen ligand containing chiral bipyrrolidine and benzimidazole moieties was prepared. The structure of C1 was confirmed by ESI-MS and