Organic Reactions Enabled by Mechanical Force‐Induced Single Electron Transfer

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(47)

Published: June 18, 2024

Mechanochemical reactions, achieved through milling, grinding, or other mechanical actions, have emerged as a solvent-free alternative to traditional solution-based chemistry. Mechanochemistry not only provides the opportunity eliminate bulk solvent use, reducing waste generation, but also unveils new reaction strategy which enables realization of reactions previously inaccessible in solution. While majority organic facilitated by force traditionally follow two-electron transfer pathways similar their counterparts, field mechanochemically induced single-electron (SET) has witnessed rapid development. This review outlines examples mechanochemical SET process, focusing on reagents that initiate SET, thereby positioning mechanochemistry burgeoning within realm

Language: Английский

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Refining the Distinct Cu–N₄ Coordination in Mesoporous N-Doped Carbon to Boost Selective Deuteration under Mild Conditions

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

Deuterated compounds have broad applications across various fields, with dehalogenative deuteration serving as an efficient method to obtain these molecules. However, the diverse electronic structures of active sites in heterogeneous system and limited recyclability homogeneous significantly hinder advancement deuteration. In this study, we present a catalyst composed copper single-atom anchored within ordered mesoporous nitrogen-doped carbon matrix, synthesized via mesopore confinement method. The Cu1/OMNC-1100 catalyst, characterized by Cu-N4 sites, demonstrates exceptional performance, high functional group tolerance, remarkable durability 2-bromo-6-methoxynaphthalene under relatively mild conditions (80 °C, 2 MPa CO). Experimental results combined X-ray absorption fine structure analysis reveal that Cu-N3 can be converted into more stable counterparts at higher pyrolysis temperatures, resulting enhanced catalytic activity. This work strategy for designing site catalysts tunable coordination environments, providing promising approach improving performance selective reactions conditions.

Language: Английский

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Overcoming High Reduction Potentials via Consecutive Mechanical-Force-Induced Electron Transfer Strategy

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Mechanical-force-induced redox catalysis has recently advanced rapidly, emerging as a green and innovative tool in synthetic chemistry. The foundation of this strategy lies the single electron transfer (SET) from polarized piezoelectric materials to substrates, which is initiated by potential generated through mechanical agitation. magnitude primarily influenced intrinsic properties material. In certain circumstances, however, may be insufficient trigger SET process, akin limitations visible-light excitation photocatalytic reactions. This challenge motivated us explore effective solutions. work, we establish catalytic system that utilizes consecutive mechanical-force-induced (ConMET) strategy. novel employs mechanochemical catalysts, with 9-phenyl-dihydroacridine (D1) serving sacrificial donors, facilitating produce significantly more powerful reductive species during grinding. Our approach effectively promotes reduction aryl iodides, bromides even electron-rich chlorides, possess potentials high − 2.8 V (vs. SCE), leading formation radicals. Ultimately, enables anti-Markovnikov hydroarylation alkenes dehalogenative deuteration aromatic halides (Cl, Br) under mild conditions.

Language: Английский

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Mechanoredox-Enabled Isothiocyanation of Primary Amines Using Piezoelectric Material as the Redox Catalyst

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

Published: Feb. 7, 2025

A novel mechanoredox-enabled synthesis of aromatic and aliphatic isothiocyanates from primary amines carbon disulfide under ball milling conditions using a piezoelectric material (BaTiO3) as the redox catalyst has been developed. This method displays several features, such short reaction time, operational simplicity, room temperature air conditions, minimal solvent, broad substrate scope, recyclable cheap catalyst. Preliminary mechanistic studies revealed that highly polarized acted single-electron transfer (SET) oxidation reagent for key desulfurization process.

Language: Английский

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The First Recyclable Molecular Ferroelectric Can Catalyze Difunctionalization of Olefin

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

Abstract Ferroelectrics have great potential for applications in catalysis due to their spontaneous polarization. Despite the advantages of molecular ferroelectrics contrast inorganic ferroelectric catalysts, has been rarely investigated. The difunctionalization alkenes is widely used organic chemistry construct complex molecules, while its conventional synthesis methods tend be poorly selective or require harsh reaction conditions and catalysts suffer from limited durability. Here, first time, TMCM‐CdCl 3 (TMCM = Me NCH 2 Cl) as a catalyst hydroxysulfurization aryl olefins under ultrasonic stimulation, which shows high selectivity, ultrahigh atom utilization, good yield. Meanwhile, substrates needed this strategy are cheap readily available, such non‐activated thiophenols without pre‐functionalization green reagent oxygen air. More importantly, can easily recycled an aqueous solution maintain catalytic performance after 50 cycles, showing long‐term surface domains released charges ultrasound, promoting hydroxyl sulphation reaction. It known that report recyclable ferroelectric‐catalyzed olefin difunctionalization, opens up new pathway olefin.

Language: Английский

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Pd-catalyzed deuteration of aryl halides with deuterium oxide

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 16, 2025

Late-stage deuteration of aryl halides with deuterium oxide is a highly desirable but challenging transformation, primarily due to the difficulty activating inert carbon-halogen bonds and umpolung in presence various functional groups. To achieve this efforts have been made develop photo-chemical, electro-chemical, or mechano-chemical strategies. However, these approaches often require specialized setups activated substrates. Despite well-known group tolerance palladium catalysis, which makes it valuable late-stage functionalization, palladium-catalyzed has remained elusive. Herein, reaction bromides, chlorides, triflates developed, through catalysis. Chemical equivalent amount D2O required for substrates like chlorides. The features high tolerance, making suitable deuteration. authors report catalyzed oxide.

Language: Английский

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Mechanochemical Activation of Aryl Diazonium Salts: Synthesis of Polycyclic (Hetero)Aromatics

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12197 - 12203

Published: Aug. 20, 2024

Although the synthesis of polycyclic (hetero)aromatics via [4 + 2] benzannulation process has been thoroughly explored, restricted availability energy sources (including thermal, light, and electrical energy) mandates utilization substantial quantities organic solvents, inevitably leading to environmental pollution, resource wastage, low reaction efficiency. Herein, we report a new method for from diazonium salts alkynes under ball-milling conditions. This mechanochemical approach requires only substoichiometric amounts DMSO as liquid-assisted grinding additive furnishes desired product in short time.

Language: Английский

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Mechanically Induced Cationic Reversible Addition-Fragmentation Chain Transfer Polymerization of Vinyl Ethers

Chemical Science, Journal Year: 2024, Volume and Issue: 15(45), P. 18977 - 18984

Published: Jan. 1, 2024

The cationic RAFT polymerization of vinyl ethers, driven by a mechanoredox process, has been successfully demonstrated, allowing for the synthesis well-defined poly(vinyl ether) under solvent-free and ambient conditions.

Language: Английский

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