Substrate-Photocatalyst Reactivity Matching Enables Broad Aryl Halide Scope in Light-Driven, Reductive Cross-Electrophile Coupling Using ¹³C NMR as a Predictor

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 8103 - 8113

Published: May 1, 2025

Language: Английский

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Cobalt-catalyzed reductive alkynylation to construct C(sp)-C(sp3) and C(sp)-C(sp2) bonds

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(7), P. 109283 - 109283

Published: Nov. 9, 2023

Language: Английский

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Multiphoton‐driven Photocatalytic Defluorination of Persistent Perfluoroalkyl Substances and Polymers by Visible Light

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(42)

Published: June 19, 2024

Abstract Perfluoroalkyl substances (PFASs) and fluorinated polymers (FPs) have been extensively utilized in various industries, whereas their extremely high stability poses environmental persistence difficulty waste treatment. Current decomposition approaches of PFASs FPs typically require harsh conditions such as heating over 400 °C. Thus, there is a pressing need to develop new technique capable decomposing them under mild conditions. Here, we demonstrated that perfluorooctanesulfonate (PFOS), known “persistent chemical,” Nafion, widely sulfonated FP for ion‐exchange membranes, can be efficiently decomposed into fluorine ions ambient via the irradiation visible LED light onto semiconductor nanocrystals (NCs). PFOS was completely defluorinated within 8‐h 405‐nm light, turnover number C−F bond dissociation per NC 17200. Furthermore, 81 % defluorination Nafion achieved 24‐h irradiation, demonstrating efficient photocatalytic properties light. We revealed this driven by cooperative mechanisms involving light‐induced ligand displacements Auger‐induced electron injections hydrated electrons higher excited states. This study not only demonstrates feasibility breaking down but also paves way advancing toward sustainable fluorine‐recycling society.

Language: Английский

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Efficient Synthesis and Iodine‐Functionalization of Pyrazoles via KIO3/PhSeSePh System under Acidic Conditions

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: 19(23)

Published: Aug. 20, 2024

Abstract This manuscript reports a novel method for the direct iodination of C‐4 pyrazole ring generated in situ by reaction 1,1,3,3‐tetramethoxypropane and various hydrazines. In this approach, potassium iodate (KIO 3 ) is used as iodinating agent (PhSe) 2 catalysts under acidic conditions. protocol provides convenient efficient synthesis 4‐iodo‐1‐aryl‐1 H ‐pyrazoles, valuable intermediates several different coupling reactions.

Language: Английский

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Electrochemical NiH‐Catalyzed C(sp³)−C(sp³) Coupling of Alkyl Halides and Alkyl Alkenes

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(44)

Published: Sept. 14, 2023

Abstract Herein, an electrochemically driven NiH‐catalyzed reductive coupling of alkyl halides and alkenes for the construction C sp 3 −C bonds is firstly reported. Notably, serve dual function as substrates hydrogen sources to generate NiH species under electrochemical conditions. The tunable nature this reaction realized by introducing intramolecular coordinating group substrate, where product can be easily adjusted give desired branched products. method proceeds mild conditions, exhibits a broad substrate scope, affords moderate excellent yields with over 70 examples, including late‐stage modification natural products drug derivatives. Mechanistic insights offer evidence process. ‐carbon‐halogen activated through single electron transfer (SET) nickel catalyst in its low valence state, generated cathodic reduction, generation from pivotal transformation.

Language: Английский

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Visible-Light-Mediated Diels-Alder Reactions Under Single-Chain Polymer Confinement: Investigating the Role of the Crosslinking Moiety on Catalyst Activity

Published: Sept. 14, 2023

Macromolecular scaffolds are rapidly emerging in catalysis owing to the ability control catalyst placement at precise locations framework. This often allows for cooperation multi-catalytic reactions that may not be observed using small molecules, enabling high levels of reactivity. Herein, we describe a triphenylpyrylium (TPT)-based visible-light active single-chain polymer nanoparticle (SCNP) scaffold facilitates radical cation [4+2]-cycloaddition. In our studies, find catalytic activity is highly dependent on identity crosslinking group – incorporated 5-10% overall its act as redox mediator Diels-Alder reaction. Mechanistic studies indicate vast majority TPT excited states quenched by acene, with resultant formed from either naphthalene- or phenanthrene-based SCNPs able proceed oxidizing dienophile elementary step reaction, leading near quantitative yields cycloadduct. The TPT-SCNP demonstrates enhanced reactivity low loadings when compared molecule TPT, and also recycled reused three iterations reaction prior substantial drops yield photobleaching. Our results suggest feature multiple subtle design elements can use catalysts diffusion-limited reactions.

Language: Английский

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Metallaphotocatalytic Platforms Based on Covalent Organic Frameworks for Cross‐Coupling Reactions

ChemCatChem, Journal Year: 2023, Volume and Issue: 16(7)

Published: Dec. 20, 2023

Abstract Cooperation of transition metal catalysis with photocatalysis is an emerging powerful approach to achieve coupling reactions for the synthesis important chemicals. Owing their facilely modulated structures and properties via reticular chemistry, photoactive covalent organic frameworks (COFs) arise quickly in building metallaphotocatalytic platforms targeting more efficient sustainable protocol. In this Minireview, we summarize recent advances COFs‐based (integrated) forge carbon‐carbon/heteroatom (C, B, N, O, P, S, etc.) bonds a variety cross‐coupling driven by light, focuses on engineering COFs’ backbone, as well organization mode COFs site promoted catalytic performance. We also highlight essential role underlying electron/energy processes metallated (M@COFs). Aiming guide catalysts’ design performance or currently challenging transformations, give our perspectives under‐developed yet promising field.

Language: Английский

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FeS quantum dots: preparation, structure and optical properties

Published: March 18, 2024

Transition metal chalcogenides (TMCs) have wide-ranging applications in nanoelectronics and optoelectronics due to their unique energy band structure excellent properties. Iron(Ⅱ) sulfide quantum dots (FeS QDs) are environmentally friendly semiconductor material exhibit near-infrared properties because of narrow bandgap, which is essential for infrared detectors. In this paper, FeS QDs were prepared by liquid phase ultrasonic exfoliation the solution was spin-coated on a quartz substrate form film. The morphology, structural optical solutions films studied. demonstrated good dispersion with average particle size height approximately 11.7 10.4 nm, respectively. calculated 12.7 nm using Debye-Scherrer formula, agreement TEM characterization. ultraviolet-visible-near (UV-Vis-NIR) characterization exhibited obvious absorption ultraviolet wavelength band, stable band. photoluminescence (PL) revealed luminescence peak position appeared be red-shifted an increase excitation wavelength, suggests wavelength-dependent characteristics can potentially used photovoltaic photodetector.

Language: Английский

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Ni-Catalyzed C–C Bond Forming Cross-Coupling of Aryl/Alkyl Halides with a Quantum Dots Photocatalyst

Synfacts, Journal Year: 2023, Volume and Issue: 19(10), P. 1026 - 1026

Published: Sept. 14, 2023

Key words quantum dots - nickel catalysis photocatalysis electrophile cross-coupling

Language: Английский

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