Sustainability Assessment of Mechanochemistry by Using the Twelve Principles of Green Chemistry

ChemSusChem, Год журнала: 2021, Номер 14(10), С. 2145 - 2162

Опубликована: Апрель 9, 2021

In recent years, mechanochemistry has been growing into a widely accepted alternative for chemical synthesis. addition to their efficiency and practicality, mechanochemical reactions are also recognized sustainability. The association between Green Chemistry often originates from the solvent-free nature of most protocols, which can reduce waste production. However, satisfies more than one Principles Chemistry. this Review we will present series examples that clearly illustrate how significantly contribute fulfillment in holistic manner.

Язык: Английский

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Mechanochemical Cross-Coupling Reactions

Trends in Chemistry, Год журнала: 2020, Номер 2(12), С. 1066 - 1081

Опубликована: Окт. 20, 2020

Язык: Английский

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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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Tackling Solubility Issues in Organic Synthesis: Solid-State Cross-Coupling of Insoluble Aryl Halides

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(16), С. 6165 - 6175

Опубликована: Март 30, 2021

Conventional organic synthesis generally relies on the use of liquid solvents to dissolve reactants. Therefore, reactions sparingly soluble or insoluble substrates are challenging and often ineffective. The development a solvent-independent solid-state approach that overcomes this longstanding solubility issue would provide innovative synthetic solutions access new areas chemical space. Here, we report extremely fast highly efficient palladium-catalyzed Suzuki-Miyaura cross-coupling via high-temperature ball-milling technique. This protocol enables cross-couplings aryl halides with large polyaromatic structures barely reactive under conventional solution-based conditions. Notably, discovered luminescent material strong red emission. was prepared coupling Pigment violet 23, compound has so far not been involved in molecular transformations due its low solubility. study thus provides practical method for accessing unexplored space through compounds cannot be carried out by any other approach.

Язык: Английский

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Mechanoredox Chemistry as an Emerging Strategy in Synthesis

Chemistry - A European Journal, Год журнала: 2021, Номер 27(38), С. 9721 - 9726

Опубликована: Апрель 1, 2021

Abstract Recent research endeavors have established that the mechanochemical activation of piezoelectric materials can open new avenues in redox chemistry. Impact forces, such as those imparted by a ball mill, been shown to transform barium titanate (BaTiO 3 ) into highly polarized state, which then donate an electron suitable oxidant and receive from reductant, mimicking photoredox catalytic cycles. Proof‐of‐concept studies elucidated mechanoredox chemistry holds great potential sustainable efficient radical‐based synthesis.

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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Mechanochemistry-Directed Ligand Design: Development of a High-Performance Phosphine Ligand for Palladium-Catalyzed Mechanochemical Organoboron Cross-Coupling

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(12), С. 6823 - 6837

Опубликована: Март 9, 2023

Mechanochemical synthesis that uses transition-metal catalysts has attracted significant attention due to its numerous advantages, including low solvent waste, short reaction times, and the avoidance of problems associated with solubility starting materials. However, even though mechanochemical environment is largely different from homogeneous solution systems, catalysts, which were originally developed for use in solution, have been used directly reactions without any molecular-level modifications ensure their suitability mechanochemistry. Alas, this limited development more efficient cross-coupling processes. Here, we report a conceptually distinct approach, whereby mechanochemistry-directed design develop ligands Suzuki-Miyaura reactions. The ligand was guided by experimental observation catalyst deactivation via aggregation palladium species, problem particularly prominent solid-state By embedding into poly(ethylene glycol) (PEG) polymer, found phosphine-ligated palladium(0) species could be immobilized fluid phase created PEG chains, preventing physical mixing crystalline solid thus undesired deactivation. This catalytic system showed high activity polyaromatic substrates close room temperature. These usually require elevated temperatures reactive presence systems conventional such as SPhos. present study hence provides important insights high-performance potential inspire industrially attractive, almost solvent-free technologies.

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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Solid‐State Radical C−H Trifluoromethylation Reactions Using Ball Milling and Piezoelectric Materials

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(50), С. 22570 - 22576

Опубликована: Сен. 14, 2020

Abstract The application of piezoelectricity for the generation trifluoromethyl (CF 3 ) radicals is reported together with development a method mechanochemical C−H trifluoromethylation aromatic compounds. As compared to conventional solution‐based approaches, this mechanoredox enables cleaner and more sustainable access wide range trifluoromethylated N‐heterocycles peptides, which are important structural motifs in modern drug discovery. This study thus represents an milestone future applications systems medicinal pharmaceutical science.

Язык: Английский

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