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1.
Phys Chem Chem Phys ; 26(2): 873-878, 2024 Jan 03.
Article in English | MEDLINE | ID: mdl-38087913

ABSTRACT

Mechanochemical reactions sometimes give different yields from those under solvent conditions, and such mechanochemical reactivities depend on the reactions. This study theoretically elucidates what governs mechanochemical reactivities, taking the Diels-Alder reactions as an example. Applying mechanical force can be regarded as the deformation of molecules, and the deformation in an orthogonal direction to a reaction mode can lower the reaction barrier. Here, we introduce a dimensionless cubic force constant, a mechanochemical reaction constant. It tells us how easily the deformation can lower a reaction barrier and enables us to compare the mechanochemical reactivities of different reactions. The constants correlate positively with the yields of the mechanochemical Diels-Alder reactions.

2.
Chem Sci ; 14(27): 7475-7481, 2023 Jul 12.
Article in English | MEDLINE | ID: mdl-37449073

ABSTRACT

We demonstrate the use of a metal surface to directly catalyse copper-catalysed alkyne-azide click-coupling (CuAAC) reactions under the conditions of Resonant Acoustic Mixing (RAM) - a recently introduced and scalable mechanochemical methodology that uniquely eliminates the need for bulk solvent, as well as milling media. By using a simple copper coil as a catalyst, this work shows that direct mechanocatalysis can occur in an impact-free environment, relying solely on high-speed mixing of reagents against a metal surface, without the need for specially designed milling containers and media. By introducing an experimental setup that enables real-time Raman spectroscopy monitoring of RAM processes, we demonstrate 0th-order reaction kinetics for several selected CuAAC reactions, supporting surface-based catalysis. The herein presented RAM-based direct mechanocatalysis methodology is simple, enables the effective one-pot, two-step synthesis of triazoles via a combination of benzyl azide formation and CuAAC reactions on a wide scope of reagents, provides control over reaction stoichiometry that is herein shown to be superior to that seen in solution or by using more conventional CuCl catalyst, and is applied for simple gram-scale synthesis of the anticonvulsant drug Rufinamide.

3.
J Phys Chem A ; 127(28): 5790-5794, 2023 Jul 20.
Article in English | MEDLINE | ID: mdl-37409965

ABSTRACT

Mechanochemical reactions sometimes yield unexpected products or product ratios in comparison to conventional reaction conditions. In the present study, we theoretically reveal the origin of the mechanochemical selectivity by considering the Diels-Alder reaction of diphenylfulvene and maleimide as an example. The application of an external force is equivalent to the production of a structural deformation. Here, we show that a mechanical force applied in a direction orthogonal to the reaction mode can lower the activation barrier by varying the potential energy curvature in the transition state. In the case of the Diels-Alder reaction, the endo-type pathway was found to be more mechanochemically favorable than the exo-type pathway, which is consistent with the experimental observations.

4.
Chem Commun (Camb) ; 59(8): 1010-1013, 2023 Jan 24.
Article in English | MEDLINE | ID: mdl-36546478

ABSTRACT

Resonant acoustic mixing (RAM) enables mechanoredox catalysis with BaTiO3 as the piezoelectric catalyst on model diazonium coupling reactions. RAM proceeds without formal grinding or impact media, is faster than the analogous ball-milling strategy, and is readily scalable. X-ray diffraction and spectroscopy indicate that reusability of BaTiO3 as a mechanoredox catalyst under ball-milling or RAM might be limited by boration.


Subject(s)
Acoustics , Catalysis
6.
Faraday Discuss ; 241(0): 128-149, 2023 Jan 05.
Article in English | MEDLINE | ID: mdl-36239309

ABSTRACT

Resonant acoustic mixing (RAM) offers a simple, efficient route for mechanochemical synthesis in the absence of milling media or bulk solvents. Here, we show the use of RAM to conduct the copper-catalysed coupling of sulfonamides and carbodiimides. This coupling was previously reported to take place only by mechanochemical ball milling, while in conventional solution environments it is not efficient, or does not take place at all. The results demonstrate RAM as a suitable methodology to conduct reactions previously accessed only by ball milling and provide a detailed, systematic overview of how the amount of liquid additive, measured by the ratio of liquid volume to weight of reactants (η, in µL mg-1), can affect the course of a mechanochemical reaction and the polymorphic composition of its product. Switching from ball milling to RAM allowed for the discovery of a new polymorph of the model sulfonylguanidine obtained by catalytic coupling of di(cyclohexyl)carbodiimide (DCC) and p-toluenesulfonamide, and the ability to control reaction temperature in RAM enabled in situ control of the polymorphic behaviour of this nascent product. We show that the reaction conversion for a given reaction time does not change monotonically but, instead, achieves a maximum for a well-defined η-value. This "η-sweet-spot" of conversion is herein designated ηmax. The herein explored reactions demonstrate sensitivity to η on the order of 0.01 µL mg-1, which corresponds to an amount of liquid additive below 5 mol% compared to the reactants, and is at least one to two orders of magnitude lower than the η-value typically considered in the design of liquid-assisted ball milling mechanochemical reactions. Such sensitivity suggests that strategies to optimise liquid-assisted mechanochemical reactions should systematically evaluate η-values at increments of 0.01 µL mg-1, or even finer. At η-values other than ηmax the reaction conversion drops off, demonstrating that the same liquid additive can act either as a catalyst or an inhibitor of a mechanochemical reaction, depending on the amount.

7.
Angew Chem Int Ed Engl ; 61(13): e202115030, 2022 03 21.
Article in English | MEDLINE | ID: mdl-35138018

ABSTRACT

We demonstrate catalytic organic synthesis by Resonant Acoustic Mixing (RAM): a mechanochemical methodology that does not require bulk solvent or milling media. Using as model reactions ruthenium-catalyzed ring-closing metathesis and copper-catalyzed sulfonamide-isocyanate coupling, RAM mechanosynthesis is shown to be faster, operationally simpler than conventional ball-milling, while also providing the first example of a mechanochemical strategy for ruthenium-catalyzed ene-yne metathesis. Reactions by RAM are readily and directly scaled-up without any significant changes in reaction conditions, as shown by the straightforward 200-fold scaling-up of the synthesis of the antidiabetic drug Tolbutamide, from hundreds of milligrams directly to 30 grams.


Subject(s)
Ruthenium , Acoustics , Catalysis , Chemistry Techniques, Synthetic , Copper
8.
Molecules ; 26(18)2021 Sep 18.
Article in English | MEDLINE | ID: mdl-34577138

ABSTRACT

Green Chemistry has become in the last two decades an increasing part of research interest. Nonconventional «green¼ sources for chemical reactions include micro-wave, mechanical mixing, visible light and ultrasound. 1,2,3-triazoles have important applications in pharmaceutical chemistry while their 1,2,4 counterparts are developed to a lesser extent. In the review presented here we will focus on synthesis of 1,2,3 and 1,2,4-triazole systems by means of classical and « green chemistry ¼ conditions involving ultrasound chemistry and mechanochemistry. The focus will be on compounds/scaffolds that possess biological/pharmacophoric properties. Finally, we will also present the formal cycloreversion of 1,2,3-triazole compounds under mechanical forces and its potential use in biological systems.


Subject(s)
Triazoles , Click Chemistry
10.
J Org Chem ; 81(20): 9802-9809, 2016 10 21.
Article in English | MEDLINE | ID: mdl-27679874

ABSTRACT

5-Substituted-3-(alkoxycarbonyl)alkyl-hydantoin derivatives were prepared by mechanochemistry from amino esters or dipeptides, via a 1,1'-carbonyldiimidazole-mediated one-pot/two-step cyclization reaction involving amino acid unsymmetrical urea A and carboxy-imidazolyl-dipeptide ester B intermediates. Comparative experiments in solution were also performed. The successful preparation of an antibacterial agent precursor was also investigated.

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