Metal–Organic Frameworks (MOFs): The Next Generation of Materials for Catalysis, Gas Storage, and Separation

Journal of Inorganic and Organometallic Polymers and Materials, Journal Year: 2023, Volume and Issue: 33(7), P. 1757 - 1781

Published: May 11, 2023

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

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(12), P. 6823 - 6837

Published: March 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.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 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.

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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Mechanochemically Generated Calcium‐Based Heavy Grignard Reagents and Their Application to Carbon–Carbon Bond‐Forming Reactions

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(41)

Published: July 20, 2022

In sharp contrast to the use of conventional magnesium-based Grignard reagents (R-MgX), application calcium-based heavy (R-CaX) in organic synthesis remains poorly explored. This is mainly due lack experimentally simple ways access such organocalcium nucleophiles from readily available starting materials under mild conditions. Here, we show that a mechanochemical technique using ball milling allows generation aryl halides and commercially calcium metal without complicated pre-activation processes. Notably, all experimental operations can be carried out air. Our operationally protocol enables rapid development novel cross-electrophile-coupling reactions mediated by arylcalcium nucleophiles, which are rather difficult reagents. method will allow synthetic chemists unique reactivity nucleophiles.

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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Mechanophotocatalysis: A Generalizable Approach to Solvent‐minimized Photocatalytic Reactions for Organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Jan. 24, 2024

This proof-of-concept study cements the viability and generality of mechanophotocatalysis, merging mechanochemistry photocatalysis to enable solvent-minimized photocatalytic reactions. We demonstrate transmutation four archetypal solution-state reactions a environment driven by combined actions milling, light, photocatalysts. The chlorosulfonylation alkenes pinacol coupling aldehydes ketones were conducted under solvent-free conditions with competitive or superior efficiencies their analogues. Furthermore, decarboxylative alkylations are shown function efficiently conditions, while photoinduced energy transfer promoted [2+2] cycloaddition chalcone experiences significant initial rate enhancement over its variant. work serves as platform for future discoveries in an underexplored field: validating that is not only generalizable photocatalysis, but can also offer valuable advantages.

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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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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