Green metrics in mechanochemistry

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(19), P. 6680 - 6714

Published: Jan. 1, 2023

The quantitative assessment of the greenness mechanochemical processes for green metrics were calculated is herein reported. A general introduction to topic, variables influencing reaction outcome and, an outlook are also provided.

Language: Английский

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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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Tinkering with Mechanochemical Tools for Scale Up

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

Published: April 28, 2023

Mechanochemistry provides an environmentally benign platform to develop more sustainable chemical processes by limiting raw materials, energy use, and waste generation while using physically smaller equipment. A continuously growing research community has steadily showcased examples of beneficial mechanochemistry applications at both the laboratory preparative scale. In contrast solution-based chemistry, mechanochemical have not yet been standardized, thus scaling up is still a nascent discipline. The purpose this Minireview highlight similarities, differences challenges various approaches that successfully applied for range scales. We hope provide discussion starting point those interested in further developing commercial use and/or industrialisation.

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 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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Mechanochemical-assisted decarboxylative sulfonylation of α,β-unsaturated carboxylic acids with sodium sulfinate salts

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(5), P. 2721 - 2729

Published: Jan. 1, 2024

Herein, we report a mechanochemical-assisted decarboxylative sulfonylation of α,β-unsaturated carboxylic acids with sodium sulfinate salts using potassium iodide as an activator under water-assisted grinding conditions.

Language: Английский

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Navigating Ball Mill Specifications for Theory‐to‐Practice Reproducibility in Mechanochemistry

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Aug. 16, 2024

Abstract The rising prospects of mechanochemically assisted syntheses hold promise for both academia and industry, yet they face challenges in understanding and, therefore, anticipating respective reaction kinetics. Particularly, dependencies based on variations milling equipment remain little understood globally overlooked. This study aims to address this issue by identifying critical parameters through kinematic models, facilitating the reproducibility mechanochemical reactions across most prominent mills laboratory settings, namely planetary mixer mills. Through a series selected experiments replicating major classes organic, organometallic, transition metal‐catalyzed, inorganic from literature, we rationalize independence kinetics when accumulated energy criterion is met. As step forward facilitate practicability our findings, provide freely accessible online tool [†] that allows calculation different Our work advances current mechanochemistry lays foundation future rational exploration rapidly evolving field.

Language: Английский

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Ball-milling-enabled nickel-catalyzed radical relayed reductive cross-coupling

Cell Reports Physical Science, Journal Year: 2024, Volume and Issue: 5(2), P. 101831 - 101831

Published: Feb. 1, 2024

Nickel-catalyzed radical relayed dicarbofunctionalizations of olefins, utilizing carbon electrophiles as coupling partners, present a powerful strategy for the streamlined construction aliphatic structures. However, traditional solution-phase methods encounter challenges such need bulk solvents, limited long reaction times, and air-/moisture-sensitive reagents. As an alternative strategy, ball-mill-enabled metal-catalyzed cross-coupling reactions have gained attention due to their high reactivity atomic efficiency. While many are single- two-component methodologies, three-component solid-state remain relatively scarce. In this work, we report first, our knowledge, ball-milling-enabled Ni-catalyzed reductive dicarbofunctionalization alkenes. Two distinct readily available electrophiles, Csp2 Csp3 halides, simultaneously installed across variety olefins at room temperature in highly regioselective manner withing 1.5 h. By harnessing benefits ball milling reactions, anticipate further advancements sustainable efficient synthetic methodologies.

Language: Английский

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Mechanochemical Deracemization: A Sustainable Approach to Enantiopurity

Chemistry - A European Journal, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 3, 2025

Abstract We introduce mechanochemical deracemization (MCDR) as a novel strategy for obtaining enantiopure compounds. This study demonstrates the successful transposition of six archetypical reactions from solvent‐based to solvent‐minimized ball milling environment. The scope includes ketone, isoindolinones, imines, an ester, and inorganic compound, all which deracemized successfully. Key parameters such material, number size, use bulk material liquid‐assisted grinding (LAG) were systematically investigated, revealing their crucial role. Quantitative enantiomeric excesses (ee) achieved, while reaction times reduced by up 97 % solvent consumption much 100 %. work establishes MCDR versatile, sustainable pathway By highlighting generalizability this approach its huge potential minimizing waste, provides foundation future advancements in deracemization.

Language: Английский

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Induction-heated ball-milling: a promising asset for mechanochemical reactions

Physical Chemistry Chemical Physics, Journal Year: 2023, Volume and Issue: 25(35), P. 23435 - 23447

Published: Jan. 1, 2023

While ball-milling is becoming one of the common tools used by synthetic chemists, an increasing number studies highlight that it possible to further expand nature and products which can be synthesized, heating reaction media during mechanochemical reactions. Hence, developing set-ups enabling milling combined important target, has been looked into in both academic industrial laboratories. Here, we report a new approach for up reactions, using induction (referred as i-BM). Our set-up attractive not only because enables very fast medium (reaching ≈80 °C just 15 s), directly adaptable commercially-available equipment, but also either walls jars or beads themselves, depending on choice materials compose them. Importantly, possibility heat "from inside" (when example PMMA jar stainless steel beads) unique feature compared previously proposed systems. Through numerical simulations, then show finely tune properties this system (e.g. rate maximum temperature reached), playing with characteristics and/or conditions used. Lastly, examples applications i-BM are given, showing how help elucidate mechanisms ball-milling, synthesize molecules, control physical media.

Language: Английский

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