Mechanochemistry: New Tools to Navigate the Uncharted Territory of “Impossible” Reactions

ChemSusChem, Год журнала: 2022, Номер 15(17)

Опубликована: Июль 21, 2022

Mechanochemical transformations have made chemists enter unknown territories, forcing a different chemistry perspective. While questioning or revisiting familiar concepts belonging to solution chemistry, mechanochemistry has broken new ground, especially in the panorama of organic synthesis. Not only does it foster "thinking outside box", but also opened reaction paths, allowing overcome weaknesses traditional exactly where use well-established solution-based methodologies rules out progress. In this Review, reader is introduced an intriguing research subject not yet fully explored and waiting for improved understanding. Indeed, study mainly focused on that, although impossible solution, become possible under mechanochemical processing conditions, simultaneously entailing innovation expanding chemical space.

Язык: Английский

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Green metrics in mechanochemistry

Chemical Society Reviews, Год журнала: 2023, Номер 52(19), С. 6680 - 6714

Опубликована: Янв. 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.

Язык: Английский

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Salient Achievements in Synthetic Organic Chemistry Enabled by Mechanochemical Activation

Synthesis, Год журнала: 2023, Номер 55(16), С. 2439 - 2459

Опубликована: Май 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

Язык: Английский

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Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF

Science, Год журнала: 2023, Номер 381(6655), С. 302 - 306

Опубликована: Июль 20, 2023

All fluorochemicals—including elemental fluorine and nucleophilic, electrophilic, radical fluorinating reagents—are prepared from hydrogen fluoride (HF). This highly toxic corrosive gas is produced by the reaction of acid-grade fluorspar (>97% CaF 2 ) with sulfuric acid under harsh conditions. The use to produce fluorochemicals via a process that bypasses HF desirable but remains an unsolved problem because prohibitive insolubility . Inspired calcium phosphate biomineralization, we herein disclose protocol treating dipotassium (K HPO 4 mechanochemical affords solid composed crystalline K 3 (HPO )F 2− x Ca y (PO F) b , which found suitable for forging sulfur-fluorine carbon-fluorine bonds.

Язык: Английский

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Tinkering with Mechanochemical Tools for Scale Up

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(44)

Опубликована: Апрель 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.

Язык: Английский

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Contemporary Approaches for Amide Bond Formation

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(24), С. 4359 - 4391

Опубликована: Ноя. 7, 2023

Abstract Amide bond construction has garnered significant interest in recent decades due to amides being one of the most prevalent functional groups among bioactive molecules. Out thirty‐seven new drugs approved by FDA 2022, eleven are small molecules containing at least amide bond. Additionally, there nineteen large as drugs, some which have peptide structures, and therefore, also bear bonds. In years, multiple teams embraced challenge developing more efficient methods for formation. This dedication led numerous publications appearing monthly prestigious journals, showcasing advancements this field. The primary goal review is present viable strategies constructing It crucial differentiate between formation synthesis; hence, focus on describing specific forming C(O)−N particular, concentrates developed within last six years. There a particular emphasis approaches that consider thought process when selecting starting materials groups. approach ensures coverage all common chemical transformations yield

Язык: Английский

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Mechanochemical Approach for Air‐Tolerant and Extremely Fast Lithium‐Based Birch Reductions in Minutes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(21)

Опубликована: Март 22, 2023

Birch reduction has been widely used in organic synthesis for over half a century as powerful method to dearomatize arenes into 1,4-cyclohexadiene derivatives. However, the conventional reaction using liquid ammonia requires laborious procedures ensure inert conditions and low temperatures. Although several ammonia-free modifications have reported, development of an operationally simple, efficient, scalable protocol remains challenge. Herein, we report lithium-based air without special operating ball-milling technique. This is characterized by its operational simplicity extremely short time (within 1 min), probably owing situ mechanical activation lithium metal, broad substrate scope, no requirement dry bulk solvents. The potential our flash also demonstrated efficient bioactive target molecules gram-scale synthesis.

Язык: Английский

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Intermediates in Mechanochemical Reactions

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Янв. 5, 2024

Abstract Mechanochemical reactions offer methodological and environmental advantages for chemical synthesis, constantly attracting attention within the scientific community. Besides unmistakable sustainability advantages, conditions under which mechanochemical occur, namely solventless conditions, sometimes facilitate isolation of otherwise labile or inaccessible products. Despite these limited knowledge exists regarding mechanisms types intermediates involved. Nevertheless, in an expanding number cases, ex situ monitoring techniques have allowed observation, characterization, reaction transformations. In this Minireview, we present a series examples reactive been detected spanning organic, organometallic, inorganic, materials chemistry. Many were stabilized by non‐covalent interactions, played pivotal role guiding We believe that uncovering understanding such instances, growing mechanochemistry community could find novel opportunities catalysis discover new while achieving simplification design.

Язык: Английский

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Minireview: Ni–Fe and Ni–Co Metal–Organic Frameworks for Electrocatalytic Water‐Splitting Reactions

Small Structures, Год журнала: 2022, Номер 4(6)

Опубликована: Ноя. 27, 2022

Electrolysis is one of the clean, environmentally friendly, and sustainable pathways to produce hydrogen for renewable energy storage. However, make electrolysis a competitive technology production, developing nonprecious metal‐based catalysts oxygen evolution reaction (OER) mandatory. Several new classes electrocatalysts are developed with outstanding OER catalytic activity, stability, commercial viability. Owing structural diversity, porosity, accessibility catalytically active metal centers, nickel‐based metal–organic frameworks (MOFs) intensively explored as catalysts. In particular, bi‐ trimetallic Ni MOFs Fe Co additional nodes show excellent activity which can be tailored through fine tuning compositions. Herein, current state research in Ni‐based catalyst materials alkaline presented. Strategies improve performance like compositional variations, choice synthetic routes, support Furthermore, activities compared presented based on metrics (current density, overpotential, Tafel slopes). Finally, concluding remarks featuring key findings possible rooms future developments summarized.

Язык: Английский

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Direct mechanocatalysis by resonant acoustic mixing (RAM)

Chemical Science, Год журнала: 2023, Номер 14(27), С. 7475 - 7481

Опубликована: Янв. 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

Язык: Английский

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