Metal‐Free C‐X Functionalization in Solid‐State via Photochemistry in Ball Mills DOI Creative Commons
Carolina Spula,

Valentin Becker,

Gregor Talajić

et al.

ChemSusChem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 15, 2024

We report the first metal- and catalyst-free protocol for facile cross-coupling of aryl halides towards C-B, C-P C-S bonds under solid-state ball milling conditions via UV light irradiation. The reactions can be performed in absence bulk solvents at room temperature a mixer mill, yielding up to 99 % being tolerant various functionalized (X=I or Br). Furthermore, we developed novel photoreactor design increasing intensity. With this could demonstrate that our surpasses classical solvent based as well purely mechanochemical approaches terms green metrics energy efficiency.

Language: Английский

Salient Achievements in Synthetic Organic Chemistry Enabled by Mechanochemical Activation DOI
Eusebio Juaristi, C.G. Ávila-Ortíz

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

Citations

52
Intermediates in Mechanochemical Reactions DOI
Karen J. Ardila‐Fierro, José G. Hernández

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Jan. 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.

Language: Английский

Citations

27
Navigating Ball Mill Specifications for Theory‐to‐Practice Reproducibility in Mechanochemistry DOI Creative Commons
Orein F. Jafter, Sol Lee, Jongseong Park

et al.

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

Citations

6
Mechanochemical Cyclotrimerization: A Versatile Tool to Covalent Organic Frameworks with Tunable Stacking Mode DOI Creative Commons

Stefanie Hutsch,

Allison Leonard,

Sven Graetz

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: April 29, 2024

Abstract We introduce the first mechanochemical cyclotrimerization of nitriles, a facile strategy for synthesizing triazine‐containing molecules and materials, overcoming challenges related to carbonization solubility. Conducting this solid‐state approach in mixer ball mill with 4‐Methylbenzonitrile, we synthesize Tris(4‐methylphenyl)‐1,3,5‐triazine quantitatively as little 90 minutes. Just fast, method facilitates synthesis covalent triazine framework CTF‐1 using 1,4 Dicyanobenzene. Material characterization confirms its porous (650 m 2 g −1 ) crystalline nature. Adjusting induced mechanical energy allows control over obtained stacking conformation resulting CTFs ‐ from staggered AB arrangement an eclipsed AA conformation. Finally, substrate scope demonstrates versatility approach, successfully yielding various CTFs.

Language: Английский

Citations

5
Mechano-photoexcitation for organic synthesis using mechanoluminescent materials as photon sources DOI

Xiaobin Xin,

Jianzhao Geng, Duo Zhang

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 14, 2024

Language: Английский

Citations

4
Real‐Time In Situ Raman Monitoring of Photomechanochemical Reactions DOI Open Access
Ivica Cvrtila, Vjekoslav Štrukil, Marija Alešković

et al.

Chemistry - Methods, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 31, 2025

Abstract In its ongoing development, mechanochemistry is becoming equipped with additional energy inputs such as light. this work we demonstrate a proof‐of‐principle setup for real‐time in situ Raman monitoring of photomechanochemical reactions. Using photoisomerization azobenzenes, and photolysis adamantane diazirine model reactions, show that multiple cycles can be performed monitored ball mill, highlight reaction selectivity achieved by photomechanochemistry.

Language: Английский

Citations

0
Green aspects of mechanochemistry DOI
Davor Margetić

Elsevier eBooks, Journal Year: 2025, Volume and Issue: unknown, P. 53 - 82

Published: Jan. 1, 2025

Language: Английский

Citations

0
Manual Grinding and Sunlight Synergistically Promoted Sulfonylation of Alkenyl Sulfonium Salts with Sulfinic Acids DOI
Lihua Yang, Lin Chen, Weijun Yao

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 10, 2025

An environmentally friendly and practical method for the synthesis of various vinyl sulfones was developed through direct sulfonylation alkenyl sulfonium salts with sulfinic acids. The reaction effectively triggered by combined actions milling, sunlight, photocatalysts under solvent-free conditions, offering advantages such as a short time (5-10 min), room temperature, straightforward workup procedure. Preliminary mechanistic studies suggested that sulfonyl radical may be involved in this mechanophotocatalytic transformation process.

Language: Английский

Citations

0
Solution is not the only solution: nanographenes by mechanochemistry DOI
Mihaiela C. Stuparu

Trends in Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

Citations

0
Mechanoactivated amorphization and photopolymerization of styryldipyryliums DOI Creative Commons
Junichi Usuba, Zhenhuan Sun, Han Nguyen

et al.

Communications Materials, Journal Year: 2024, Volume and Issue: 5(1)

Published: June 8, 2024

Abstract Conventional topochemical photopolymerization reactions occur exclusively in precisely-engineered photoactive crystalline states, which often produces high-insoluble polymers. To mitigate this, here, we report the mechanoactivation of photostable styryldipyrylium-based monomers, results their amorphization-enabled solid-state and soluble processable amorphous A combination nuclear magnetic resonance, X-ray diffraction, absorption/fluorescence spectroscopy reveals crucial role a mechanically-disordered monomer phase yielding polymers via photo-induced [2 + 2] cycloaddition reaction. Hence, amorphization can expand scope polymerization conditions to open up opportunities for generating that are otherwise difficult synthesize analyze.

Language: Английский

Citations

3