Salient Achievements in Synthetic Organic Chemistry Enabled by Mechanochemical Activation

Synthesis, Journal Year: 2023, Volume and Issue: 55(16), P. 2439 - 2459

Published: May 3, 2023

Abstract Although known for millennia, it is only recently that mechanochemistry has received serious attention by chemists. Indeed, during the past 15 years an extraordinary number of reports concerning solid-state chemical transformations through grinding and milling techniques have been recorded. This short review discusses circumstances led this renaissance, highlighting present intense interest in so-called green chemistry, enabling capacity to handle insoluble substrates, identification profound influence additives can on mechanochemically activated reactions. The core account focuses salient developments synthetic organic especially amino acid peptide­ mechanosynthesis, successful employment mechanochemical activation combination with asymmetric organocatalysis, promising enzymatic whole cell biocatalysis, remarkable achievement multicomponent selective reactions via complex, multistep reaction pathways, mechanosynthesis representative heterocycles. final section comments some pending tasks area, such as scaling-up processes be practical use industry, requirement easier more efficient control parameters monitoring devices, consequently careful analysis additional procedures a proper understanding phenomena. 1 Introduction 2 Brief History Mechanochemistry 3 Milling Equipment Reaction Parameters 4 Attributes That Propelled Its Present Renaissance 4.1 Enormous Attention Being Presently Paid Sustainable Chemistry 4.2 Reduced Energy Consumption 4.3 Additive-Based 4.4 Handling Insoluble Reactants 4.5 ‘Impossible’ Reactions Are Successful 4.6 Air- Water-Sensitive Reagents Ball 5 Salient Developments Mechanochemical Activation Synthetic Organic 5.1 Amino Acid Peptide Mechanosynthesis 5.2 Asymmetric Synthesis Organocatalysis under Ball-Milling Conditions 5.3 Mechanoenzymology 5.4 Multicomponent Activated 5.5 Heterocycles Modification 6 Future Directions 6.1 Scaling-Up Protocols 6.2 Temperature-Controlled 6.3 Understanding Transformations 6.4 Emerging Techniques 7 Conclusions

Language: Английский

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Temperature‐Controlled Mechanochemistry for the Nickel‐Catalyzed Suzuki–Miyaura‐Type Coupling of Aryl Sulfamates via Ball Milling and Twin‐Screw Extrusion.**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(44)

Published: Sept. 9, 2022

Abstract The use of temperature‐controlled mechanochemistry to enable the mechanochemical nickel‐catalyzed Suzuki–Miyaura coupling is herein described. Transitioning from a capricious room‐temperature protocol, through heated, PID‐controlled programmable jar heater manifold was required deliver an efficient method for aryl sulfamates (derived ubiquitous phenols) and boronic acid species. Furthermore, this process conducted using base‐metal nickel catalyst, in absence bulk solvent, air/moisture sensitive reaction set‐ups. This methodology showcased translation large‐scale twin‐screw extrusion enabling 200‐fold scale increase, producing decagram quantities C−C coupled material.

Language: Английский

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The Direct Mechanocatalytic Suzuki–Miyaura Reaction of Small Organic Molecules

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(34)

Published: May 31, 2022

Abstract The molecular Suzuki cross‐coupling reaction was conducted mechanochemically, without solvents, ligands, or catalyst powders. Utilizing one catalytically active palladium milling ball, products could be formed in quantitative yield as little 30 min. In contrast to previous reports, the adjustment of parameters led complete elimination abrasion from thus enabling first reported systematic analysis. XPS, situ XRD, and reference experiments provided evidence that ball surface location catalysis, allowing a mechanism proposed. versatility approach demonstrated by extending substrate scope deactivated even sterically hindered aryl iodides bromides.

Language: Английский

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Direct mechanocatalysis by resonant acoustic mixing (RAM)

Chemical Science, Journal Year: 2023, Volume and Issue: 14(27), P. 7475 - 7481

Published: Jan. 1, 2023

We demonstrate the use of a metal surface to directly catalyse copper-catalysed alkyne-azide click-coupling (CuAAC) reactions under conditions Resonant Acoustic Mixing (RAM) - recently introduced and scalable mechanochemical methodology that uniquely eliminates need for bulk solvent, as well milling media. By using simple copper coil catalyst, this work shows direct mechanocatalysis can occur in an impact-free environment, relying solely on high-speed mixing reagents against surface, without specially designed containers introducing experimental setup enables real-time Raman spectroscopy monitoring RAM processes, we 0th-order reaction kinetics several selected CuAAC reactions, supporting surface-based catalysis. The herein presented RAM-based is simple, effective one-pot, two-step synthesis triazoles

Language: Английский

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The Sonogashira Coupling on Palladium Milling Balls—A new Reaction Pathway in Mechanochemistry

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(27)

Published: April 5, 2023

Abstract Utilizing direct mechanocatalytical conditions, the Sonogashira coupling was successfully performed on surface of milling tools by using pure Pd and coated steel balls. The optimization co‐catalyst forming additives led to a protocol, which generates quantitative yields under aerobic conditions for various substrates within as little 90 minutes. Using state‐of‐the‐art spectroscopic, diffractive, well in situ methods lead identification previously unknown highly reactive complex copper. This new differs substantially from known complexes liquid phase couplings, proving that reaction pathways mechanochemistry may differ those established synthetic procedures.

Language: Английский

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Photocatalytic fuel cell self-powered sensor for Cu2+ detection in water and soil: Signal amplification of biomass induced carbon-rich carbon nitride photoanode

Sensors and Actuators B Chemical, Journal Year: 2023, Volume and Issue: 395, P. 134501 - 134501

Published: Aug. 25, 2023

Language: Английский

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The Regioselective Solid‐State Photo‐Mechanochemical Synthesis of Nanographenes with UV light

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: Feb. 24, 2023

Photochemical reactors inherently suffer from the low penetration depth of light and therefore rely on high dilutions to enable chemical reactions. Here we present first method UV (ultraviolet) photochemistry in complete absence bulk solvents a ball mill. Triphenylene was synthesized by two routes, Mallory reaction cyclodehydrochlorination (CDHC), resulting yields 81 92 %, respectively. The successfully scaled up gram scale robustness demonstrated for several different substrates. Finally, regioselective assembly nanographenes mechanochemistry larger systems. Thus, mechanochemical approach presented here provides powerful new tool atomically precise construction nanographenes.

Language: Английский

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Recent developments in polymer semiconductors with excellent electron transport performances

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review describes the design considerations, bonding modes between monomers, structural modification strategies, and applications of polymer semiconductors with excellent electron transport performances.

Language: Английский

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Intramolecular direct arylation through mechanochemistry: efficient synthesis of corannulene-based peri-annulated curved nanographenes

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

Language: Английский

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Milling Medium‐Free Suzuki Coupling by Direct Mechanocatalysis: From Mixer Mills to Resonant Acoustic Mixers**

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(65)

Published: July 28, 2023

Here we describe the development of a sustainable and cost-effective approach for catalytic cross-coupling reactions in mechanochemistry. It is found that substrate's impact with vessel wall alone sufficient to initiate reaction, thus indicating milling balls function primarily as mixing agent direct mechanocatalytic Suzuki coupling. The absence can be offset by adjusting rheology using liquid-assisted grinding (LAG). LAG sweet spot 0.25 μL mg-1 confirmed both resonance acoustic mixers (RAMs) ball-free mixer mills, higher than presence balls. RAMs exhibit excellent performance achieving yields 90 % after 60 min complete conversion min. longevity significantly improved RAM, allowing at least 20 without deterioration.

Language: Английский

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