Salient Achievements in Synthetic Organic Chemistry Enabled by Mechanochemical Activation

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

---

A review on sustainable iron oxide nanoparticles: syntheses and applications in organic catalysis and environmental remediation

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(13), P. 7579 - 7655

Published: Jan. 1, 2024

In this review paper, recent developments of iron oxide nanoparticles are highlighted and discussed in the field organic catalysis environmental remediation.

Language: Английский

---

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

---

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

---

Mechanochemical Cyclotrimerization: A Versatile Tool to Covalent Organic Frameworks with Tunable Stacking Mode

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

---

Mechanochemistry in Organic Synthesis: An Italian Journey through Innovations

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(30)

Published: May 18, 2024

Abstract Mechanochemistry, as an enabling technology, harnesses mechanical force to drive chemical reactions, presenting compelling advantages in organic synthesis within the principles of green chemistry. This review explores how its unique and alignment with sustainable practices have been widely developed different scientific fields Italy. As a transformative strategy for synthesis, mechanochemistry has portrayed this valuable synthetic alternative due various advantages, such solvent reduction new reaction pathways, that use brings. Nonetheless, improvements brought about by also crucial other chemistry described Italian scientists. In whole context, researchers analysed both already optimised processes feasible paving way avenues previously hampered all limitations belong in‐solution

Language: Английский

---

Allylation of C‐, N‐, and O‐Nucleophiles via a Mechanochemically‐Driven Tsuji–Trost Reaction Suitable for Late‐Stage Modification of Bioactive Molecules

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 6, 2023

Abstract We present the first solvent‐free, mechanochemical protocol for a palladium‐catalyzed Tsuji–Trost allylation. This approach features exceptionally low catalyst loadings (0.5 mol %), short reaction times (<90 min), and simple setup, eliminating need air or moisture precautions, making process highly efficient environmentally benign. introduce solid, nontoxic, easy‐to‐handle allyl trimethylammonium salts as valuable alternative to volatile hazardous reagents. Our enables allylation of various O ‐, N C ‐nucleophiles in yields up 99 % even structurally complex bioactive compounds, owing its mild conditions exceptional functional group tolerance.

Language: Английский

---

Applications

Elsevier eBooks, Journal Year: 2025, Volume and Issue: unknown, P. 83 - 177

Published: Jan. 1, 2025

---

Listening to the Formation of Polymorphs in a Ball Mill

Analytical Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

In this contribution, we apply our newly developed ball-milling operando platform, which combines Raman spectroscopy and thermal (IR) imaging, as well acoustic high-speed optical video recordings, to the synthesis transformation of citric acid–isonicotinamide (1:2) cocrystal polymorphs in transparent PMMA jars. Particularly, demonstrate how Raman, temperature, acoustic, data are complementary enable detection connection chemical physical events happening during a time-resolved manner. Importantly, show that formation three can be detected through analyses solely. Even more impressively, meticulous sound allowed subtle polymorphic transitions perceived mode when was not conclusive enough. Such changes signatures greatly linked beads' motions milling jar. A new analysis methodology recordings is proposed combination energetic statistical approaches simplifies for potential users. The interpretation signals further validated thanks videos recorded synchronization with all other techniques. Finally, broaden opaque stainless-steel jars, showing relevance method following transformations cocrystals, pure substances, any type

Language: Английский

---

Mechanochemistry for the Sustainable Synthesis of Organic Hole Transport Materials in Perovskite Solar Cells

Crystal Growth & Design, Journal Year: 2025, Volume and Issue: unknown

Published: March 31, 2025

Mechanochemical coupling reactions are typically single-site events that thermally driven, require an inert atmosphere, and kinetically slow under ball milling conditions. Here, we demonstrate the rapid 4-fold single-pot mechanochemical C–N of tetrabromopyrene phenothiazine leading to a novel pyrene-phenothiazine (PYR–PTZ) molecule is shown be effective hole-transport material (HTM) in perovskite solar cell (PSC). When compared previously reported reactions, mechanosynthesis PYR–PTZ achieved just 99 min ball-milling ambient conditions without glovebox or need for external heating. This represents advance over previous methods synthesis HTMs opens new avenues exploring discovery other organic PSC applications. The photophysics, crystal structure, electron transport properties HTM have been characterized using combination experimental density functional theory methods. In encapsulated PSC, photoconversion efficiency comparable widely used spiro-MeOTAD molecule, but stability superior naked after 4 weeks. work demonstrates value mechanochemistry sustainable at significantly reduced costs, opening up opportunities optoelectronics.

Language: Английский

---