NIR-II emissive anionic copper nanoclusters with intrinsic photoredox activity in single-electron transfer

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 1, 2024

Abstract Ultrasmall copper nanoclusters have recently emerged as promising photocatalysts for organic synthesis, owing to their exceptional light absorption ability and large surface areas efficient interactions with substrates. Despite significant advances in cluster-based visible-light photocatalysis, the types of transformations that can catalyze remain limited date. Herein, we report a structurally well-defined anionic Cu 40 nanocluster emits second near-infrared region (NIR-II, 1000−1700 nm) after photoexcitation conduct single-electron transfer fluoroalkyl iodides without need external ligand activation. This photoredox-active efficiently catalyzes three-component radical couplings alkenes, iodides, trimethylsilyl cyanide under blue-LED irradiation at room temperature. A variety fluorine-containing electrophiles nucleophile be added onto an array including styrenes aliphatic olefins. Our current work demonstrates viability using readily accessible metal establish photocatalytic systems high degree practicality reaction complexity.

Language: Английский

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Silylarylation of Alkenes via meta-Selective C–H Activation of Arenes under Ruthenium/Iron Cooperative Catalysis: Mechanistic Insights from Combined Experimental and Computational Studies

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4510 - 4522

Published: March 12, 2024

Organosilicons are privileged skeletons in the domains of pharmaceutical chemistry, organic synthesis, and materials science. Hence, investigating catalytic techniques for synthesis organosilicon compounds has received a great deal emphasis. Carbosilylation alkenes is an efficient technique to introduce diverse molecular architectures containing silicon into chemical space. However, organohalides pseudohalides prerequisites most existing carbosilylation protocols. On other hand, utilization C–H activation been sowing seeds successful development intricate scaffolds. In this regard, synthetic accessibility complexed derivatives by through meta-C–H approach remained intangible. Herein, we present three-component strategy arylsilylation olefins with (het)arenes silanes integrating iron-catalyzed silyl radical generation, coupled intrinsic reactivity alkene, ruthenium-catalyzed functionalization (het)arene, leading targeted cross-coupled carbosilylated product. addition, theoretical investigations state-of-the-art dispersion corrected density functional theory at B3PW91-D3/Def2TZVP/CPCM(PhCF3) shed intriguing insights on selectivity probable mechanistic pathway underexplored cooperative 3d/4d transition metal catalysis, such as formation its addition alkene catalyzed iron, followed meta-selective ruthenium bound arene, furnishing C4 substituted (het)arene functionalized compounds.

Language: Английский

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Site-selective carbonylation of arenes via C(sp2)-H thianthrenation: Palladium-catalyzed direct access to α,β-unsaturated ketones

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 432, P. 115454 - 115454

Published: March 20, 2024

Language: Английский

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Base-Promoted Ring-Opening Hydroxylation of Cyclic Sulfonium Salts

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 3084 - 3091

Published: Feb. 9, 2024

Herein, we reported a general strategy for the synthesis of sulfur-containing primary alcohol derivatives by base-promoted ring-opening hydroxylation cyclic sulfonium salts. A variety salts were successfully transformed into desired hydroxylated products in moderate to excellent yields with good functional group tolerance. Moreover, one-pot synthesis, scale-up reaction, and late-stage functionalization complex molecules demonstrated practicability this synthetic protocol field chemistry.

Language: Английский

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Visible-Light-Induced Excited-State Copper Catalysis: Recent Advances and Perspectives

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 11974 - 11989

Published: July 26, 2024

Photoactive copper complexes have gained significant attention due to their photocatalytic activities. Different homogeneous Cu(I) complexes, Cu(II) and heterogeneous copper-based photocatalysts been investigated utilized in a broad spectrum of organic transformations. These applications span radical additions, C–C bond C–heteroatom cross-couplings, aerobic oxidative reactions, kinetic resolutions. This review summarizes the advancements this dynamic field visible-light-induced, excited-state copper-catalyzed reactions over recent years. It is organized according type excited species involved provides perspective on current future developments.

Language: Английский

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Recent advances in copper-catalyzed multicomponent reactions with photoinduction

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 528, P. 216428 - 216428

Published: Jan. 4, 2025

Language: Английский

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Towards a more Sustainable Photocatalysis using Copper and Iron

Current Opinion in Green and Sustainable Chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 100998 - 100998

Published: Jan. 1, 2025

Language: Английский

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Late-Stage C–H Functionalization of Dehydroalanine-Containing Peptides with Arylthianthrenium Salts and Its Application in Synthesis of Tentoxin Analogue

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 14, 2025

Dehydrophenylalanine has a characteristic unsaturated double bond that makes it indispensable in the context of peptides and proteins. In this study, we report Pd-catalyzed C(sp2)-H arylation dehydroalanine-containing with arylthianthrenium salts under mild base free conditions, which provides efficient access to dehydrophenylalanine-containing peptides. This approach enables coupling different drug scaffolds bioactive molecules Remarkably, method could be used for concise synthesis tentoxin its analogue.

Language: Английский

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Synthesis of Quinoxalines through Cu-electrocatalytic Azidation/Annulation Cascade at Low Catalyst Loading

Organic Letters, Journal Year: 2023, Volume and Issue: 25(31), P. 5896 - 5901

Published: July 29, 2023

A Cu-electrocatalytic azidation of N-aryl enamines and subsequent denitrogenative annulation for the construction quinoxaline frameworks is reported. Only 0.5 mol % copper(II) chloride was employed this cascade transformation displaying excellent functional-group compatibility even with complex bioactive scaffolds. The efficient electro-oxidative protocol enables use NaN3 as cheapest azide source. Detailed mechanistic experiments, cyclic voltammetry, spectroscopic studies provided strong evidence a dual role Cu catalyst in azidyl iminyl radical generation steps.

Language: Английский

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Modular and Practical 1,2‐Aryl(Alkenyl) Heteroatom Functionalization of Alkenes through Iron/Photoredox Dual Catalysis**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 13, 2023

Abstract Efficient methods for synthesizing 1,2‐aryl(alkenyl) heteroatomic cores, encompassing heteroatoms such as nitrogen, oxygen, sulfur, and halogens, are of significant importance in medicinal chemistry pharmaceutical research. In this study, we present a mild, versatile practical photoredox/iron dual catalytic system that enables access to highly privileged pharmacophores with exceptional efficiency site selectivity. Our approach exhibits an extensive scope, allowing the direct utilization wide range commodity or commercially available (hetero)arenes well activated unactivated alkenes diverse functional groups, drug scaffolds, natural product motifs substrates. By merging iron catalysis photoredox cycle, vast array alkene functionalization products incorporate neighboring azido, amino, halo, thiocyano nitrooxy group were secured. The scalability ability rapid synthesize numerous bioactive small molecules from readily starting materials highlight utility protocol.

Language: Английский

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