Real‐Time In Situ Raman Monitoring of Photomechanochemical Reactions

Chemistry - Methods, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 31, 2025

Abstract In its ongoing development, mechanochemistry is becoming equipped with additional energy inputs such as light. this work we demonstrate a proof‐of‐principle setup for real‐time in situ Raman monitoring of photomechanochemical reactions. Using photoisomerization azobenzenes, and photolysis adamantane diazirine model reactions, show that multiple cycles can be performed monitored ball mill, highlight reaction selectivity achieved by photomechanochemistry.

Language: Английский

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Mechano-photoexcitation for organic synthesis using mechanoluminescent materials as photon sources

Nature Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 14, 2024

Language: Английский

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Visible-light or sunlight photoredox-catalyzed β-selective acylation of alkenes to access α, β-unsaturated ketones

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A general method for accessing α,β-unsaturated ketones through visible-light or sunlight photoredox-catalyzed β-selective acylation of alkenes has been developed.

Language: Английский

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Photomechanochemistry: harnessing mechanical forces to enhance photochemical reactions

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 458 - 472

Published: March 3, 2025

Photomechanochemistry, i.e., the merger of light energy and mechanical forces, is emerging as a new trend in organic synthesis, enabling unique reactivities fleeting excited states under solvent-minimized conditions. Despite its transformative potential, field faces significant technological challenges that must be addressed to unlock full capabilities. In this Perspective, we analyze selected examples showcase available technologies combine including manual grinding, vortex shaker mixing, rod milling, ball milling. By examining advantages limitations each approach, aim provide an overview current state synthetic photomechanochemistry identify opportunities for future advancements rapidly evolving area research.

Language: Английский

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Manual Grinding and Sunlight Synergistically Promoted Sulfonylation of Alkenyl Sulfonium Salts with Sulfinic Acids

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

Published: April 10, 2025

An environmentally friendly and practical method for the synthesis of various vinyl sulfones was developed through direct sulfonylation alkenyl sulfonium salts with sulfinic acids. The reaction effectively triggered by combined actions milling, sunlight, photocatalysts under solvent-free conditions, offering advantages such as a short time (5-10 min), room temperature, straightforward workup procedure. Preliminary mechanistic studies suggested that sulfonyl radical may be involved in this mechanophotocatalytic transformation process.

Language: Английский

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A scalable photo-mechanochemical platform for sustainable photoredox catalysis by resonant acoustic mixing

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

Published: April 28, 2025

Photocatalysis has greatly advanced in organic synthesis but still confronts challenges, including light attenuation reaction media and excessive solvent utilization. These issues lead to inefficiencies, particularly heterogeneous cloudy mixtures scaling-up applications. Integrating photocatalysis with mechanochemistry offers a nascent promising solution these challenges. Herein, we present scalable photo-mechanochemical platform that combines visible-light Resonant Acoustic Mixing (RAM), enabling efficient cross-coupling reactions under solvent-minimised conditions. This approach demonstrates broad substrate tolerance, accommodating variety of aryl (hetero) halides N-, O-, P-, S-nucleophiles. The protocol supports scaling up 300 mmol, representing 1500-fold increase, while maintaining exceptionally low catalyst loading achieving 9800 turnover numbers (TON). generality this is further validated by its applicability other synthetic transformations.

Language: Английский

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Mechanometallaphotoredox Catalysis: Utilizing Increased Throughput Mechanochemistry to Develop Solvent-Minimized Aryl Amination and C(sp2)-C(sp3) Cross-Coupling Reactions with Increased Tolerance to Aerobic Conditions

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 22, 2025

Photocatalysis as a tool used in organic synthesis has predominantly relied on the use of solvents, be it under homogeneous or heterogeneous conditions. In particular, metallaphotoredox catalysis reactions commonly toxic solvents such DMA and DMF. Herein, we demonstrate how mechanophotocatalysis, synergistic union mechanochemistry photocatalysis, is compatible with this class dual involving both photocatalyst nickel(II) cocatalysts. Using ball milling, these mechanistically complex can conducted absence bulk solvent air, affording high-yielding aryl aminations C(sp2)-C(sp3) cross-couplings alkyl carboxylic acids, trifluoroborate salts, bromides. These advances are facilitated by introduction novel reaction vessel design for conducting four mechanophotocatalysis simultaneously. This work highlights promise solvent-minimized photocatalysis reactions, demonstrating that examples redundant, thus significantly reducing waste stream. Through time-resolved photoluminescence studies, observed excited states five different photocatalysts were quenched oxygen more solution than solid state, providing evidence origin increased tolerance to aerobic conditions experience.

Language: Английский

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Metal‐Free C‐X Functionalization in Solid‐State via Photochemistry in Ball Mills

ChemSusChem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 15, 2024

We report the first metal- and catalyst-free protocol for facile cross-coupling of aryl halides towards C-B, C-P C-S bonds under solid-state ball milling conditions via UV light irradiation. The reactions can be performed in absence bulk solvents at room temperature a mixer mill, yielding up to 99 % being tolerant various functionalized (X=I or Br). Furthermore, we developed novel photoreactor design increasing intensity. With this could demonstrate that our surpasses classical solvent based as well purely mechanochemical approaches terms green metrics energy efficiency.

Language: Английский

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Mechanochemical Radical Transformations in Organic Synthesis

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 22, 2024

Abstract Organic synthesis has historically relied on solution‐phase, polar transformations to forge new bonds. However, this paradigm is evolving, propelled by the rapid evolution of radical chemistry. Additionally, organic witnessing a simultaneous resurgence in mechanochemistry, formation bonds solid‐state, further contributing shift status quo. The aforementioned advances chemistry have predominantly occurred solution phase, while majority mechanochemical feature transformations. Herein, we discuss rapidly advancing area synthesis: reactions. Solid‐state reactions offer improved green metrics, better reaction outcomes, and access intermediates products that are difficult or impossible reach solution. This review explores these context small molecule synthesis, from early findings current state‐of‐the‐art, underscoring pivotal role solid‐state likely play sustainable chemical synthesis.

Language: Английский

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Mechanosynthesis of ruthenium trisbipyridyl complexes and application in photoredox catalysis in a ball-mill

RSC Mechanochemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 8, 2024

Ball-milling allowed the efficient preparation of ruthenium complexes with photoredox properties. With a transparent and chemically resistant milling jar in epoxy resin, photoreductive dehalogenation was realized efficiently solventless manner.

Language: Английский

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