A General Platform for Visible Light Sulfonylation Reactions Enabled by Catalytic Triarylamine EDA Complexes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2583 - 2592

Published: Jan. 17, 2024

Catalytic electron donor–acceptor (EDA) complexes have recently emerged as a powerful and sustainable alternative to iridium- ruthenium-based photoredox synthetic methods. Yet, these remain underexplored reliant on the use of meticulously designed acceptors that require previous installation. Herein, we report novel EDA complex employing tris(4-methoxyphenyl) amine catalytic donor for sulfonylation alkenes using inexpensive readily available sulfonyl chlorides. Applying this operationally simple, visible-light-mediated general platform, both redox-neutral net-reductive functionalization more than 60 substrates, encompassing vinylic or allylic sulfonylation, hydrosulfonylation, sulfamoylation activated unactivated alkynes.

Language: Английский

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Recent Progress and Emerging Technologies towards a Sustainable Synthesis of Sulfones

ChemSusChem, Journal Year: 2021, Volume and Issue: 14(22), P. 4878 - 4902

Published: Sept. 3, 2021

Sulfones play a pivotal role in modern organic chemistry. They are highly versatile building blocks and find various applications as drugs, agrochemicals, or functional materials. Therefore, sustainable access to this class of molecules is great interest. Herein, the goal was provide summary on recent developments field sulfone synthesis. Advances existing limitations traditional approaches towards sulfones were reviewed selected examples. Furthermore, novel emerging technologies for more synthesis future directions discussed.

Language: Английский

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Rapid and Scalable Halosulfonylation of Strain‐Release Reagents**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(3)

Published: Oct. 13, 2022

Sulfonylated aromatics are commonplace motifs in drugs and agrochemicals. However, methods for the direct synthesis of sulfonylated non-classical arene bioisosteres, which could improve physicochemical properties drug agrochemical candidates, limited. Here we report a solution to this challenge: one-pot halosulfonylation [1.1.1]propellane, [3.1.1]propellane bicyclo[1.1.0]butanes that proceeds under practical, scalable mild conditions. The sulfonyl halides used chemistry feature aryl, heteroaryl alkyl substituents, conveniently generated situ from readily available sulfinate salts halogen atom sources. This methodology enables an array pharmaceutically agrochemically relevant halogen/sulfonyl-substituted bioisosteres cyclobutanes, on up multidecagram scale.

Language: Английский

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Triboelectric Nanogenerators-Based Therapeutic Electrical Stimulation on Skin: from Fundamentals to Advanced Applications

ACS Nano, Journal Year: 2023, Volume and Issue: 17(11), P. 9793 - 9825

Published: May 30, 2023

Discovery of the amazing and vital therapeutic roles electrical stimulation (ES) on skin has sparked tremendous efforts to investigate ES suppliers. Among them, triboelectric nanogenerators (TENGs), as a self-sustainable bioelectronic system, can generate self-powered biocompatible for achieving superior effects applications. Here, brief review application TENGs-based is presented, with specific discussions fundamentals its feasibility be applied adjusting physiological pathological processes skin. Then, comprehensive in-depth depiction emerging representative applications categorized reviewed, particular descriptions about antibacterial therapy, promoting wound healing, facilitating transdermal drug delivery. Finally, challenges perspectives further advancing toward more powerful versatile strategy are discussed, particularly regarding opportunities in fundamental multidisciplinary research biomedical

Language: Английский

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Visible‐Light Induced Fixation of SO₂ into Organic Molecules with Polypyridine Chromium(III) Complexes

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(6)

Published: Jan. 23, 2023

Abstract Incorporation of sulfur dioxide into organic compounds is achieved by a photocatalytic approach using sensitizers made from earth‐abundant chromium(III) ions and visible light leading to sulfones sulfonamides. We employed three different [Cr(ddpd) 2 ] 3+ , [Cr(bpmp) [Cr(tpe) with long excited state lifetimes ground redox potentials as well varying stability under the reaction conditions (ddpd= N N’ ‐dimethyl‐ ’‐dipyridin‐2‐yl‐pyridine‐2,6‐diamine; bpmp=2,6‐bis(2‐pyridylmethyl)pyridine; tpe=1,1,1‐tris(pyrid‐2‐yl)ethane). Key steps catalytic cycles are identified electrochemical, luminescence quenching, photolysis, laser flash photolysis experiments delivering detailed picture challenges in these transformations. The reactivity reduced chromium complex was key property explain outcomes. Initial cage escape yield determinations revealed that desired photoreactions occur unusually high quantum efficiencies, whereas side reactions almost unproductive.

Language: Английский

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I₂/DMSO-mediated oxidative C–C and C–heteroatom bond formation: a sustainable approach to chemical synthesis

RSC Advances, Journal Year: 2024, Volume and Issue: 14(9), P. 5817 - 5845

Published: Jan. 1, 2024

A variety of bioactive compounds can be synthesized via C–C and C–X (X = O/S/N/Se/Cl/Br) bond formation using an efficient catalytic system I 2 /DMSO. This review highlights the progress identifies potential paths for future research in this field.

Language: Английский

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Towards an efficient selective oxidation of sulfides to sulfones by NiWO and α-AgWO

Applied Catalysis A General, Journal Year: 2023, Volume and Issue: 652, P. 119038 - 119038

Published: Jan. 13, 2023

Chemoselective oxidation of sulfides to sulfones under mild conditions is relevant for industry, but challenging owing the need establish catalysis mechanisms and optimize several experimental parameters.Herein, we report synthesis MWO 4 (M = Cd, Co, Cu, Mn, Ni, Zn) α-Ag 2 WO semiconductors as efficient selective catalysts this transformation in darkness.This catalytic process tolerant a broad range functionalized substituted even presence oxidative-sensitive functional groups.α-Ag NiWO were most with good selectivity, stability, yield very conditions.This study presents distinctive reaction mechanism process, which it different from that commonly considered, electron-hole pairs are created when UV light shone.These findings open pathway processes on complete darkness, overcoming limitation light, wide applications.

Language: Английский

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Metal–Organic Frameworks as a Tunable Platform to Deconvolute Stereoelectronic Effects on the Catalytic Activity of Thioanisole Oxidation

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 3955 - 3962

Published: Jan. 31, 2024

The local environment of a metal active site plays an important role in affecting the catalytic activity and selectivity. In recent studies, tailoring behavior molybdenum-based via modulation first coordination sphere has led to improved thioanisole oxidation performance, but disentangling electronic effects from steric influences that arise these modifications is nontrivial, especially heterogeneous systems. To this end, tunability metal–organic frameworks (MOFs) makes them promising scaffolds for controlling heterogeneous, catalytically while offering additional attractive features such as crystallinity high porosity. Herein, we report variety MOF-supported Mo species, which were investigated methyl phenyl sulfoxide and/or sulfone using tert-butyl hydroperoxide (tBHP) oxidant. particular, MOFs contrasting node architectures targeted, presenting unique opportunity investigate stereoelectronic control sites systematic manner. A Zr6-based MOF, NU-1000, was employed along with its sulfated analogue NU-1000-SO4 anchor dioxomolybdenum enabled examination support-mediated polarizability on performance. addition, MOF containing mixed node, Mo-MFU-4l, used probe impact N-donor ligand transmetalated center. Characterization techniques, including single crystal X-ray diffraction, concomitantly reaction time course profiles better comprehend dynamics different sites, thus correlating structural change activity.

Language: Английский

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Photocatalytic Radical Cascade Cyclization of N-(o-Cyanobiaryl)acrylamides with Sulfonyl Chlorides

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 2, 2025

A photoredox-catalyzed radical cascade cyclization of N-(o-cyanobiaryl)acrylamides with sulfonyl chlorides for the construction sulfonyl-containing pyrido[4,3,2-gh]phenanthridines has been disclosed. The developed synthetic tool tolerates a broad range to undergo sequence, including addition, nitrile insertion, and cyclization.

Language: Английский

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Hydrosulfonylation of Alkenes with Sulfonyl Imines via Ir/Cu Dual Photoredox Catalysis

Organic Letters, Journal Year: 2022, Volume and Issue: 24(22), P. 3944 - 3949

Published: May 26, 2022

Sulfonamides exhibit the advantages of wide prevalence, excellent prefunctionalization capability, and broad functional group compatibility. We report here utilizing sulfonyl imines as radical precursors for hydrosulfonylation activated alkenes via visible-light irradiation. By preinstallation groups into sulfonamides subsequent hydrosulfonylation, a variety complex sulfones were synthesized with good efficiency under Ir/Cu dual photoredox catalysis. Additionally, this protocol expands research in late-stage N–S bond modification sulfonamides.

Language: Английский

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