Solid-state Suzuki–Miyaura cross-coupling reactions: olefin-accelerated C–C coupling using mechanochemistry

Seo, Tamae; Ishiyama, Tatsuo; Kubota, Koji; Ito, Hajime

doi:10.1039/c9sc02185j

Cited by 105 publications

(108 citation statements)

References 61 publications

(38 reference statements)

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“…A similar preference for mechanochemical reaction conditions was previously noted for the related C−N coupling reactions of sulfonamides . Such behavior differs from, for example, bimolecular Schiff base condensations, palladium‐catalyzed Suzuki coupling reactions, or multicomponent formation of N ‐heterocycles, which often readily proceed in solution or through ball milling. Consequently, it is tempting to consider certain classes of reactions, for example, the herein‐demonstrated family of C−N coupling reactions of amides and sulfonamides, as mechanochemically favored.…”

Section: Discussionsupporting

confidence: 60%

Catalytic Room‐Temperature C−N Coupling of Amides and Isocyanates by Using Mechanochemistry

et al. 2020

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A mechanochemical route is developed for room‐temperature and solvent‐free derivatization of different types of amides into carbamoyl isatins (up to 96 % conversion or yield), benzamides (up to 81 % yield), and imides (up to 92 % yield). In solution, this copper‐catalyzed coupling either does not take place or requires high temperatures at which it may also be competing with alternative thermal reactivity, highlighting the beneficial role of mechanochemistry for this reaction. Such behavior resembles the previously investigated coupling with sulfonamide substrates, suggesting that this type of C−N coupling is an example of a mechanochemically favored reaction, for which mechanochemistry appears to be a favored environment over solution.

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Section: Discussionsupporting

confidence: 60%

Catalytic Room‐Temperature C−N Coupling of Amides and Isocyanates by Using Mechanochemistry

et al. 2020

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“…To the best of our knowledge, there are no reports on the neat mechanochemical synthesis of salen and salophen ligands and their group 13 complexes (LAG was required for full conversion) or a comprehensive scaling-up studies (Fig.2b). Inspired by concepts put forth by Ito et al, 49,50 we decided to expand our model to cover both solid-liquid and solid-solid type synthesis.…”

Section: Resultsmentioning

confidence: 99%

“…32 g of ligand required 200 mL of methanol under reflux conditions, with an additional 500 mL of diethyl ether for workup. This methodology results in high E-factors [41][42][43][44][45]49 (i.e., total weight of all the solvents used in this synthesis divided by the weight of isolated product). This severely impacts the practical industrial implementation of such complexes, since large scale synthesis leaves a large environmental footprint…”

Section: Introductionmentioning

confidence: 99%

Multi-gram Mechanosynthesis of Salophen-Complex: A Comparative Analysis

Garcı́a¹,

Ong²,

Singh³

et al. 2020

Preprint

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Mechanochemistry is a powerful alternative to traditional solvent-based synthesis as it is environmentally benign, allows for higher yields in shorter reaction times, while minimizing the use of solvents. Although mechanochemical routes are becoming increasingly mainstream in synthetic laboratories, up-scales examples for main group complexes are still rare. Here, motivated by the practical implementation of mechanosynthesis, we demonstrated the synthesis of salen and salophen complexes. The herein reported synthesis displays low E-factor and process mass intensity compared to conventional solution methods. In addition, analyses evaluating environmental parameters, energy consumption and production costs have been performed, showing the multiple advantages mechanochemistry has over convetional solution-based synthesis<br>

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“…The history and applications of mechanochemistry have been reviewed [90][91][92]. Particularly promising features of this ('Green Chemistry' [93]) method of promoting chemical changes include the absence, or much reduced amounts, of solvents and the ability to obtain commercially valuable products (e.g. sugars, aromatic compounds, etc.)…”

Section: Discussionmentioning

confidence: 99%

Thermal reactions involving solids: a personal view of selected features of decompositions, thermal analysis and heterogeneous catalysis

Galwey

2020

J Therm Anal Calorim

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Convinced that some recent trends in the literature concerned with reactions involving solids have been unproductive, even discouraging interest in the subject, this reviewer analyses the reasons and charts a way forward. In particular, two topics are discussed: thermal analysis and activation energy. Thermal analysis, automated collection and interpretation of kinetic data for solid(?)-state decompositions, resulted in huge numbers of publications between late 1970s and 2010. Measurements were frequently minimalistic (few, often no, confirmatory tests complemented rate data). Kinetic data interpretations were based on the Arrhenius activation model, inapplicable to these assumed, usually unconfirmed, solid-state(?) reactions. Energy distributions within crystalline reactants differ from those of 'free-flying' gaseous reactants, and thus, mechanistic proposals are entirely speculative. Such studies yielded little more than the reaction temperature: no meaningful insights into reaction chemistry, controls, mechanisms. Despite my several highly critical articles, these inconsequential studies continued. Overall, this now sidelined topic impacted adversely on solid-state chemistry, activation energy, E. Concurrently with the above studies, L'vov published a theoretical explanation for the magnitude of E: the Congruent Dissociative Volatilisation (CDV), thermochemical approach. This was also ignored by the 'Thermoanalytical Community', possibly because it assumes an initial volatilisation step: it appears that many solid-state scientists are prejudiced against mechanisms involving a phase change. The value of this novel theory (CDV) in identifying controls and mechanisms of solid-state reactions is discussed here. This review is positive: an interesting branch of main-stream chemistry remains open for exploration, expansion, explanation and exploitation! Publisher's Note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

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Solid-state Suzuki–Miyaura cross-coupling reactions: olefin-accelerated C–C coupling using mechanochemistry

Abstract: The first general solid-state Suzuki–Miyaura cross-coupling reactions using mechanochemistry has been developed.

Cited by 105 publications

References 61 publications

Catalytic Room‐Temperature C−N Coupling of Amides and Isocyanates by Using Mechanochemistry

Catalytic Room‐Temperature C−N Coupling of Amides and Isocyanates by Using Mechanochemistry

Multi-gram Mechanosynthesis of Salophen-Complex: A Comparative Analysis

Thermal reactions involving solids: a personal view of selected features of decompositions, thermal analysis and heterogeneous catalysis

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