Unleashing the potentiality of metals: synergistic catalysis with light and electricity

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 4024 - 4040

Published: Jan. 1, 2024

This review provides a comprehensive overview of metal catalysis in photo-electrochemical systems, discussing reaction mechanisms and offering prospects for this triadic catalytic mode.

Language: Английский

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Enantioselective Remote Alkylation Enabled by Metallaphotoredox Catalysis via Selective C–C Bond Cleavage

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 2212 - 2221

Published: Jan. 23, 2025

Despite recent advances in enantioselective radical coupling with strained cyclic rings, asymmetric reactions triggered by unstrained motifs remain rare. Herein, we report a mild and general strategy for activating diverse set of readily available alcohols the remote site-specific allylic alkylation ketones through combination photoredox-mediated proton-coupled electron transfer chiral chromium catalysis. This newly developed dual catalytic system exhibits extensive applicability, operates under conditions, offers straightforward operation, demonstrates tolerance to functional groups. The open-shell has also been applied late-stage modification complex drug natural product derivatives high levels enantioselectivity.

Language: Английский

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Boosting Ammonium Oxidation in Wastewater by the BiOCl-Functionalized Anode

Environmental Science & Technology, Journal Year: 2023, Volume and Issue: 57(49), P. 20915 - 20928

Published: Nov. 28, 2023

Mixed metal oxide (MMO) anodes are commonly used for electrochlorination of ammonium (NH4+) in wastewater treatment, but they suffer from low efficiency due to inadequate chlorine generation at Cl– concentrations and sluggish reaction kinetics between free NH4+ under acidic pH conditions. To address this challenge, we develop a straightforward wet chemistry approach synthesize BiOCl-functionalized MMO electrodes using the as an efficient Ohmic contact electron transfer. Our study demonstrates that BiOCl@MMO anode outperforms pristine anode, exhibiting higher (24.6–60.0 mg Cl2 L–1), increased Faradaic (75.5 vs 31.0%), improved rate constant oxidation (2.41 0.76 L–1 min–1) 50 mM concentration. Characterization techniques including paramagnetic resonance situ transient absorption spectra confirm production radicals (Cl• Cl2•–) by BiOCl/MMO anode. Laser flash photolysis reveals significantly apparent second-order constants ((4.3–4.9) × 106 M–1 s–1 2.0–4.0) Cl•, compared undetectable Cl2•–, well slower (102 < 4.0) within same range, emphasizing significance Cl• enhancing oxidation. Mechanistic studies provide compelling evidence capacity BiOCl adsorption, facilitating evolution generation. Importantly, exhibits excellent long-term stability high catalytic activity NH4+-N removal real landfill leachate. These findings offer valuable insights into rational design improve electrocatalytic abatement, which holds great promise treatment applications.

Language: Английский

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Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(7), P. 1595 - 1605

Published: Feb. 3, 2024

Abstract Herein, we present a photoinduced deconstructive alkoxyamination of alkyl alcohols catalyzed by iron salts. This transformation involves the initiation alkoxy radicals through chlorine radical‐induced radical formation, followed β ‐scission and trapping resulting carbon with 2,2,6,6‐tetramethylpiperidin‐1‐yl (TEMPO). reaction exhibits broad substrate scope (40 examples), including primary secondary that are prone to oxidation combination TEMPO iron. Mechanistic investigations have revealed enhanced coordination chloride ion center inhibits OH process, thereby enabling tolerance alcohols.

Language: Английский

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Mechanisms of C(sp³)-H Functionalization of Acetonitrile or Acetone with Alkynes: A DFT Investigation

Journal of Chemical Information and Modeling, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

The mechanisms for the C(sp3)-H activation and addition reactions between acetonitrile (or acetone) alkynes have been investigated with M06-2X-D3/ma-def2-TZVP method basis set. SMD (solvation model based on solute electron density) was applied to simulate solvent effect. In first second reactions, 2-phenylbut-3-yn-2-ol reacted acetone, respectively. First, activations of acetone could be achieved by PhCOO• t-BuO• radicals. Then, converted into final products P1 P2. Gibbs free energy surfaces these two suggest that blue lines would favorable paths lower barriers, terminal C atom C≡C bond is best reactive site. Moreover, analysis IRI (Interaction Region Indicator) reveals Z- E-configuration transformations. While in third fourth methyl(2-(phenylethynyl)phenyl)sulfane has interactions via some paths, profiles show C10 atom, rather than C11 priority, are favorable. Furthermore, action mode Na2HPO4 reduce barrier benefit reaction. vdW (van der Waals) play an important role choice fifth sixth) reaction, it happened 1-(2-(methylthio)phenyl)-3-phenylprop-2-yn-1-one acetontrile yield product P5 P6). computational results uncovered line path, site depends interactions, which origin selectivity. addition, investigation byproducts carried out, can explain reason only main produced. Both those agree experimental results. localized orbital locator (LOL) isosurfaces, Laplacian order (LBO), density critical point (ρBCP), spin isosurface graphs, graphs used analyze structure reveal reaction substances.

Language: Английский

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Direct conversion of cyano group to cyanogen chloride and dichloroacetonitrile in the UV/chlorine process

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 481, P. 148353 - 148353

Published: Dec. 25, 2023

Language: Английский

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Iron‐Catalyzed Oxidative C−C Bond Cleavage of Unstrained Tertiary Alkyl Aromatics to Arylketones

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(15), P. 2524 - 2529

Published: July 3, 2023

Abstract We present here an iron‐catalyzed oxidative C sp 3 −C bond cleavage of unstrained tertiary alkyl aromatics to provide a range synthetically useful arylketones even with H 2 O as the oxidant. This method is operationally simple, scalable, and eco‐friendly, well suitable for late‐stage oxidation complex molecules bearing hydroxy groups, making it valuable tool in organic synthesis.

Language: Английский

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Eco-friendly iron-catalyzed oxidation of unstrained tertiary aromatic alcohols to ketones

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(1), P. 108835 - 108835

Published: July 29, 2023

Language: Английский

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Photoinduced FeCl₃-Catalyzed Chlorination of Aromatic Sulfonyl Chloride via Extrusion of SO₂ at Room Temperature

Organic Letters, Journal Year: 2023, Volume and Issue: 25(24), P. 4576 - 4580

Published: June 8, 2023

We report, herein, a photoinduced iron-catalyzed direct chlorination of aromatic sulfonyl chloride at room temperature. In this protocol, FeCl3-catalyzed has been realized temperature under the irradiation light (400–410 nm). During process, many commercially or readily available substituted chlorides could produce corresponding in moderate to good yields.

Language: Английский

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