Heme and nonheme high-valent manganese(V)-oxo complexes: Synthesis, characterization, and reactivity

Coordination Chemistry Reviews, Год журнала: 2025, Номер 528, С. 216429 - 216429

Опубликована: Янв. 11, 2025

Язык: Английский

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Highly Position- and Enantioselective Catalytic Epoxidation of Polyolefins Mediated by a Chiral Mn Complex, Including a One-Step Conversion of Squalene to the (S)-2,3-Epoxide, a Precursor of Natural Steroids and Terpenoids

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(2), С. 1448 - 1451

Опубликована: Янв. 6, 2025

Reported herein is the synthesis of a novel chiral dicarboxylic ligand for Mn(II) and application Mn complex to highly enantio- position-selective epoxidation C═C under mild conditions, even with polyolefinic substrates. A stereomechanistic basis asymmetric induction suggested.

Язык: Английский

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Adding new dimension to non-directed C(sp3)–H functionalizations

Science China Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 3, 2025

Язык: Английский

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Redox-Active Ligands Permit Multielectron O₂ Homolysis and O-Atom Transfer at Exceptionally High-Valent Vanadyl Complexes

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 8, 2025

A five-coordinate chlorovanadium species supported by two redox-active N-phenyl aminophenol ligands was prepared. Experimental and computational data support formulation of this complex as [(Phap)(Phisq)VIVCl], containing one dianionic [Phap]2- amidophenolate monoanionic [Phisq]•- iminosemiquinonate radical. Exposure [(Phap)(Phisq)VIVCl] to O2 readily cleaves the O═O bond generate [(Phisq)(Phibq)VIV(O)Cl], an [Phibq] iminobenzoquinone, so 2e- oxidation is entirely ligand centered. [(Phisq)(Phibq)VIV(O)Cl] reduced net H2 abstraction from 9,10-dihydroanthracene, or in reactions with main-group nucleophiles, such PPh3 Me2S, which form a new oxygen regenerate [(Phap)(Phisq)VIVCl]. Accordingly, dioxygenase-type activation O-atom transfer cycling are direct consequence redox noninnocence covalency vanadium─aminophenol bonding. The donor acceptor substrates establish V≡O BDE 73 ± 14 kcal mol-1 [(Phisq)(Phibq)VIV(O)Cl]. Reported BDEs redox-innocent vanadyl complexes typically fall range 120-170 mol-1. Unlike later 3d metals, where M═O high energy activated by, for instance, occupancy M-O π* antibonding MOs, exceptionally weak [(Phisq)(Phibq)VIV-(O)Cl] reflects stabilization product. Thus, research highlights alternative pathway generating strong oxidants that not outer-sphere electron acceptors, implications design early metal catalysts aerobic oxidations acceptors X-H bonds.

Язык: Английский

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Palladium catalyzed C(sp3)–H trifluoroethoxylation

Journal of Catalysis, Год журнала: 2024, Номер 435, С. 115563 - 115563

Опубликована: Май 18, 2024

Язык: Английский

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Nonheme Fe Based Enzyme Mimics for Fine Organic Synthesis: Catalytic C−H and C=C Oxygenations

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(40)

Опубликована: Июль 8, 2024

Abstract Since the milestone contribution by Chen and White in 2007, bioinspired non‐heme bis ‐amino‐ ‐pyridylmethyl Fe complexes have been at forefront of studies related to designing catalytic approaches for direct oxidative functionalization aliphatic C−H bonds. This, however, has not developed into large‐scale synthetic applications date. The present concept is aimed briefly discussing state‐of‐the‐art catalyzed oxidations organic molecules with H 2 O , current oxidant choice oxidation catalysis, mostly focusing on oxidations, analyzing peculiarities their reactivity through prism potential fine synthesis.

Язык: Английский

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Enzymatic and Bio-inspired Enantioselective Oxidation of Non-activated C-H Bonds

Synthesis, Год журнала: 2024, Номер unknown

Опубликована: Авг. 26, 2024

Abstract The enantioselective oxidation of C–H bonds relies on two different approaches: the use enzymes or bio-inspired transition metal catalysts. Both are powerful tools, as they transform ubiquitous C(sp3)–H into valuable oxygenated building blocks. However, reaction remains a challenge in synthetic chemistry, continuously demanding efficient catalytic systems to improve substrate scopes. Optimization site- and enantioselectivities bio-catalytic is underpinned by protein engineering, while ligand design medium effects play crucial roles complexes. In this Short Review, recent advances field described, focusing reactions that target strong, non-activated bonds. 1 Introduction 1.1 Enantioselective Catalytic Oxidation Nature Bio-Inspired Systems 1.2 Biological Mechanism Challenges for Implementation Chirality with Synthetic Catalysts 1.3 Bio-Catalytic Systems: From Microorganism Engineered Enzymes 1.4 Mimicking Nature: Approach 1.5 Origin Enantioselectivity 2 Non-Activated Bonds 2.1 Hydroxylation at 2.2 Lactonization Enzymatic 2.3 2.4 Small-Molecule 3 Conclusions

Язык: Английский

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Electrochemically driven nonheme iron complex-catalyzed oxidation reactions using water as an oxygen source

Journal of Catalysis, Год журнала: 2024, Номер 440, С. 115792 - 115792

Опубликована: Окт. 16, 2024

Язык: Английский

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Direct Selective Azidation of C(sp3)−H Groups

Tetrahedron Chem, Год журнала: 2024, Номер unknown, С. 100114 - 100114

Опубликована: Ноя. 1, 2024

Язык: Английский

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