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

Polymer vessels in mechanochemical syntheses: assessing material performance DOI Creative Commons

Marisol Fabienne Rappen,

Lars Beissel,

Jonathan H. Geisler

et al.

RSC Mechanochemistry, Journal Year: 2024, Volume and Issue: 1(4), P. 386 - 392

Published: Jan. 1, 2024

This work assesses the performance of 16 polymers in mechanochemical reactions, examining six key parameters: cost-effectiveness, environmental impact, mechanical-, thermal- and chemical resistance, transparency to laser-, X-ray radiation.

Language: Английский

Citations

3

Mechanochemical Deracemization: A Sustainable Approach to Enantiopurity DOI Open Access

Job Gieling,

Guillaume Wéry,

Chrystal Lopes

et al.

Chemistry - A European Journal, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 3, 2025

Abstract We introduce mechanochemical deracemization (MCDR) as a novel strategy for obtaining enantiopure compounds. This study demonstrates the successful transposition of six archetypical reactions from solvent‐based to solvent‐minimized ball milling environment. The scope includes ketone, isoindolinones, imines, an ester, and inorganic compound, all which deracemized successfully. Key parameters such material, number size, use bulk material liquid‐assisted grinding (LAG) were systematically investigated, revealing their crucial role. Quantitative enantiomeric excesses (ee) achieved, while reaction times reduced by up 97 % solvent consumption much 100 %. work establishes MCDR versatile, sustainable pathway By highlighting generalizability this approach its huge potential minimizing waste, provides foundation future advancements in deracemization.

Language: Английский

Citations

0

Photomechanochemistry: harnessing mechanical forces to enhance photochemical reactions DOI Creative Commons
Francesco Mele, Ana Maria Constantin, Andrea Porcheddu

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 458 - 472

Published: March 3, 2025

Photomechanochemistry, i.e., the merger of light energy and mechanical forces, is emerging as a new trend in organic synthesis, enabling unique reactivities fleeting excited states under solvent-minimized conditions. Despite its transformative potential, field faces significant technological challenges that must be addressed to unlock full capabilities. In this Perspective, we analyze selected examples showcase available technologies combine including manual grinding, vortex shaker mixing, rod milling, ball milling. By examining advantages limitations each approach, aim provide an overview current state synthetic photomechanochemistry identify opportunities for future advancements rapidly evolving area research.

Language: Английский

Citations

0

A scalable photo-mechanochemical platform for sustainable photoredox catalysis by resonant acoustic mixing DOI Creative Commons

Deshen Kong,

Yi Liang, Alice Nanni

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 28, 2025

Photocatalysis has greatly advanced in organic synthesis but still confronts challenges, including light attenuation reaction media and excessive solvent utilization. These issues lead to inefficiencies, particularly heterogeneous cloudy mixtures scaling-up applications. Integrating photocatalysis with mechanochemistry offers a nascent promising solution these challenges. Herein, we present scalable photo-mechanochemical platform that combines visible-light Resonant Acoustic Mixing (RAM), enabling efficient cross-coupling reactions under solvent-minimised conditions. This approach demonstrates broad substrate tolerance, accommodating variety of aryl (hetero) halides N-, O-, P-, S-nucleophiles. The protocol supports scaling up 300 mmol, representing 1500-fold increase, while maintaining exceptionally low catalyst loading achieving 9800 turnover numbers (TON). generality this is further validated by its applicability other synthetic transformations.

Language: Английский

Citations

0

[2 + 2] photocycloaddition reaction as a tool to monitor the molecular motions in the solid state by mechanochemical grinding DOI
Jagadese J. Vittal

Journal of Photochemistry and Photobiology C Photochemistry Reviews, Journal Year: 2023, Volume and Issue: 57, P. 100636 - 100636

Published: Sept. 26, 2023

Language: Английский

Citations

8

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

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(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

3

Parameters Influencing the Photochemical Cyclodehydrochlorination (CDHC) Reaction DOI Creative Commons
Anthony Jolly, Charles‐Émile Fecteau, Paul A. Johnson

et al.

ChemPlusChem, Journal Year: 2024, Volume and Issue: 89(6)

Published: Feb. 9, 2024

Abstract The photochemical cyclodehydrochlorination (CDHC) reaction has recently been used to prepare a wide variety of polycyclic aromatic hydrocarbons and graphene nanoribbons (GNRs). However, the parameters affecting efficiency this have scarcely studied. In work, we investigated how conditions influence outcome reaction. effect functional groups on different phenyl rings o ‐terphenyl scaffold was also kinetics follow same trend as Hammett's constant when electron‐donating electron‐withdrawing are present ring bearing chlorine. CDHC can be successfully performed using less energetic 365 nm light in presence triplet sensitizer. Computational results provide insight mechanism, notably by identifying its three intermediate structures well limiting step.

Language: Английский

Citations

2

Photoredox Annulation of Polycyclic Aromatic Hydrocarbons DOI Creative Commons
Davide Zanetti,

Oliwia Matuszewska,

Giuliana Giorgianni

et al.

JACS Au, Journal Year: 2023, Volume and Issue: 3(11), P. 3045 - 3054

Published: Nov. 14, 2023

The rise of interest in using polycyclic aromatic hydrocarbons (PAHs) and molecular graphenoids optoelectronics has recently stimulated the growth modern synthetic methodologies giving access to intramolecular aryl-aryl couplings. Here, we show that a radical-based annulation protocol allows expansion planarization approaches prepare functionalized graphenoids. enabler this reaction is peri-xanthenoxanthene, photocatalyst which undergoes photoinduced single electron transfer with an ortho-oligoarylenyl precursor bearing electron-withdrawing nucleofuge groups. Dissociative enables formation persistent aryl radical intermediates, latter undergoing C-C bond formation, allowing occur. conditions are mild compatible various -donating substituents on rings as well heterocycles PAHs. method could be applied induce double reactions, synthesis π-extended scaffolds different edge peripheries.

Language: Английский

Citations

4

Mechanochemical Transformations of Pharmaceutical Cocrystals: Polymorphs and Coformer Exchange DOI
Marek J. Potrzebowski, Katarzyna Trzeciak, Marta K. Dudek

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 10, 2024

Abstract Transformations of solid samples under solvent‐free or minimal solvent conditions set the future trend and define a modern strategy for production new materials. Of various technologies tested in recent years, mechanochemical approach seems to be most promising economic ecological reasons. The aim this review article is present current state art research on binary systems, which have found numerous applications pharmaceutical materials science industries. This divided into three sections. In first part, we describe equipment improvements, include innovative application thermo‐mechanochemistry, sono‐mechanochemistry, photo‐mechanochemistry, electro‐mechanochemistry, as well resonant acoustic mixing (RAM), transformation high‐speed sample spinning (“SpeedMixing”). A brief description techniques dedicated ex‐situ in‐situ studies progress mechanism matter (PXRD, FTIR, Raman NMR spectroscopy) presented. second section, discuss problem cocrystal polymorphism highlighting issue related with correlation between parameters ( time, temperature, energy, molar ratio, used liquid assistant, surface crystal size, shape) preference formation requested polymorph. last part devoted processes coformer exchange systems forced by mechanical and/or thermal stimuli. influence thermodynamic factor selection best‐suited partner two‐component stable structure

Language: Английский

Citations

1

Mechanosynthesis of ruthenium trisbipyridyl complexes and application in photoredox catalysis in a ball-mill DOI Creative Commons
Florian Luttringer, Matthieu Lavayssiere,

Enita Rastoder

et al.

RSC Mechanochemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 8, 2024

Ball-milling allowed the efficient preparation of ruthenium complexes with photoredox properties. With a transparent and chemically resistant milling jar in epoxy resin, photoreductive dehalogenation was realized efficiently solventless manner.

Language: Английский

Citations

1