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 enabling highly efficient Birch reduction using sodium lumps and d-(+)-glucose

Chemical Science, Год журнала: 2024, Номер 15(12), С. 4452 - 4457

Опубликована: Янв. 1, 2024

In this study, a mechanochemical protocol for highly efficient and ammonia-free sodium-based Birch reduction was developed, leveraging the use of cheap easy-to-handle sodium lumps d -(+)-glucose as proton source.

Язык: Английский

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Mechanochemical synthesis of organoselenium compounds

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Янв. 26, 2024

We disclose herein a strategy for the rapid synthesis of versatile organoselenium compounds under mild conditions. In this work, magnesium-based selenium nucleophiles are formed in situ from easily available organic halides, magnesium metal, and elemental via mechanical stimulation. This process occurs liquid-assisted grinding (LAG) conditions, requires no complicated pre-activation procedures, operates broadly across diverse range aryl, heteroaryl, alkyl substrates. symmetrical diselenides efficiently obtained after work-up air, while one-pot nucleophilic addition reactions with various electrophiles allow comprehensive unsymmetrical monoselenides high functional group tolerance. Notably, method is applied to regioselective selenylation diiodoarenes polyaromatic aryl halides that difficult operate solution approaches. Besides selenium, sulfur tellurium also competent process, which showcases potential methodology facile organochalcogen compounds.

Язык: Английский

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Recent Advances in Dearomative Partial Reduction of Benzenoid Arenes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)

Опубликована: Март 14, 2024

Abstract Dearomative partial reduction is an extraordinary approach for transforming benzenoid arenes and has been well‐known many decades, as exemplified by the dehydrogenation of Birch hydroarylation Crich addition. Despite its remarkable importance in synthesis, this field experienced slow progress over last half‐century. However, a revival observed with recent introduction electrochemical photochemical methods. In Minireview, we summarize advancements dearomative arenes, including dihydrogenation, hydroalkylation, arylation, alkenylation, amination, borylation others. Further, intriguing utilization synthesis natural products also emphasized. It anticipated that Minireview will stimulate further arene transformations.

Язык: Английский

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Mechanochemistry for Organic and Inorganic Synthesis

ACS Organic & Inorganic Au, Год журнала: 2024, Номер 4(5), С. 432 - 470

Опубликована: Авг. 7, 2024

In recent years, mechanochemistry has become an innovative and sustainable alternative to traditional solvent-based synthesis. Mechanochemistry rapidly expanded across a wide range of chemistry fields, including diverse organic compounds active pharmaceutical ingredients, coordination compounds, organometallic complexes, main group frameworks, technologically relevant materials. This Review aims highlight advancements accomplishments in mechanochemistry, underscoring its potential as viable eco-friendly conventional solution-based methods the field synthetic chemistry.

Язык: Английский

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Liquid-Assisted Grinding Enables Efficient Ni-Catalyzed, Mn-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Benzyl Chlorides

Molecules, Год журнала: 2025, Номер 30(5), С. 1060 - 1060

Опубликована: Фев. 26, 2025

An efficient and air-tolerant Ni-catalyzed denitrogenative cross-electrophile coupling of benzotriazinones with benzyl chlorides has been developed via liquid-assisted grinding by using Mn powders as reductant DMF assisting liquid in the presence anhydrous calcium chloride. Scope limitations protocol to access diarylmethanes have demonstrated more than 20 examples, showing acceptable tolerance functional group steric hindrance. Although electron-withdrawing substituents on benzotriazinone or counterparts decrease yields significantly, a series N-alkyl-2-benzylbenzamides, bearing an ortho-carbamoyl aryl group, could be obtained modest good yields.

Язык: Английский

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Synthesis without solvent: consequences for mechanochemical reactivity

Chemical Communications, Год журнала: 2023, Номер 59(96), С. 14210 - 14222

Опубликована: Янв. 1, 2023

Solution-based reactions are a staple of synthetic chemistry—but what happens mechanochemically, when there is no solvent?

Язык: Английский

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Mechanochemical activation of metallic lithium for the generation and application of organolithium compounds in air

Nature Synthesis, Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

Язык: Английский

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The quest for organo-alkali metal monomers: unscrambling the structure–reactivity relationship

Dalton Transactions, Год журнала: 2023, Номер 52(24), С. 8172 - 8192

Опубликована: Янв. 1, 2023

This perspective explores the strategies that have been employed to isolate low aggregate and, in particular, monomeric complexes of most common alkali metal alkyls and relationship between aggregation, structure reactivity.

Язык: Английский

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Dearomatization of (Hetero)arenes through Photodriven Interplay between Polysulfide Anions and Formate**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(40)

Опубликована: Авг. 16, 2023

Abstract The facile construction of C(sp 3 )‐rich carbo‐ and heterocyclic compounds is a pivotal synthetic strategy to foster contemporary drug discovery programs. downstream dearomatization readily accessible two‐dimensional (2D) planar arenes represents direct pathway towards accessing three‐dimensional (3D) aliphatic scaffolds. Here, we demonstrate that polysulfide anions are capable catalyzing process substituted naphthalenes, indoles, other related heteroaromatic in the presence potassium formate methanol under visible light irradiation. developed protocol exhibits broad functional group tolerance, operational simplicity, scalability, cost‐effectiveness, representing practical sustainable tool for arene dearomatization.

Язык: Английский

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