Force-Induced Dissolution of Imaginary Mode in Mechanochemical Reaction: Dibenzophenazine Synthesis

Haruta, Naoki; Oliveira, P. M. S.; Sato, Tohru; Tanaka, Kazuyoshi; Baron, Michel

doi:10.1021/acs.jpcc.9b05582

Cited by 11 publications

(11 citation statements)

References 64 publications

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“…There is some elegance to this complexity: many of the processes which govern mechanochemical reactions of complex systems can be largely deconstructed into some combination of the elementary processes which occur in simpler systems. For example, mechanical treatment of a single powder particle will still involve geometric distortion of its molecular substituents ( Haruta et al, 2019 ), and there remains the potential for molecular or atomic electronic excitation/emission processes to occur. This behavior is clear for example in high pressure experiments of molecular solids, wherein mechanical action of the bulk lattice yields geometric ( Fabbiani et al, 2005 ) and electronic distortions ( Poręba et al, 2019 ) or excitations ( Tulip and Bates, 2009 ) at the molecular or atomic level( Boldyreva, 2019 ; Katrusiak, 2019 ; Zakharov and Boldyreva, 2019 ).…”

Section: Introductionmentioning

confidence: 99%

Tribochemistry, Mechanical Alloying, Mechanochemistry: What is in a Name?

Michalchuk

Болдырева²,

Belenguer³

et al. 2021

Front. Chem.

151

108

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Over the decades, the application of mechanical force to influence chemical reactions has been called by various names: mechanochemistry, tribochemistry, mechanical alloying, to name but a few. The evolution of these terms has largely mirrored the understanding of the field. But what is meant by these terms, why have they evolved, and does it really matter how a process is called? Which parameters should be defined to describe unambiguously the experimental conditions such that others can reproduce the results, or to allow a meaningful comparison between processes explored under different conditions? Can the information on the process be encoded in a clear, concise, and self-explanatory way? We address these questions in this Opinion contribution, which we hope will spark timely and constructive discussion across the international mechanochemical community.

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Section: Introductionmentioning

confidence: 99%

Tribochemistry, Mechanical Alloying, Mechanochemistry: What is in a Name?

Michalchuk

Болдырева²,

Belenguer³

et al. 2021

Front. Chem.

151

108

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“…The origin of rate acceleration of mechanochemical-induced DCR is worthy of more in-depth investigation. Previously, diimine formation facilitated by solid-state ball milling was reported and in situ generated water molecules were proposed to catalyze the reaction. − We attempted to carry out DCR with 1 and 2a in the presence of activated 3 Å molecular sieves. The reaction with or without a drying agent took place with more or less the same reaction rate; thus, the involvement of the water catalyst responsible for dramatic rate acceleration observed here in DCR is highly unlikely.…”

Section: Resultsmentioning

confidence: 99%

Solvent-Free Mechanochemical Diaza-Cope Rearrangement

Liu

et al. 2021

ACS Sustainable Chem. Eng.

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Chiral vicinal diamines represent an important class of organic building blocks that play essential roles in various fields in chemical and material sciences. Their syntheses have continued to attract attention to enhance their yield, selectivity, and scope, but all of the procedures reported so far in the literature are solvent-based reactions. We herein report the first example of mechanochemical diaza-Cope rearrangement to convert a wide variety of aldehyde substrates into chiral diimines, which upon hydrolysis lead to the formation of chiral vicinal diamines. This solvent-free protocol is highlighted with high yield, fast reaction, and simple synthetic operation with commercially available precursors and is easily scalable to gram quantity. Mechanistic investigations revealed a distinct reaction profile for mechanochemical-induced reactions compared to solution-based reactions. Reaction time course studies showed that the diaza-Cope rearrangement step, which requires a highly ordered six-membered chair-like TS, is rapid in mechanochemical-induced reactions. This enhanced rate stems from the formation of effective solid-state packing in mechanochemical reaction settings. The powder X-ray diffraction analysis of the milled sample confirmed the formation of a new crystalline phase during the mechanochemical reaction, which leads to continuation of the reaction even after ball milling is stopped. Furthermore, we developed a one-pot two-step procedure to synthesize chiral salen metal complexes, a “privileged” chiral catalyst, directly from arylaldehydes without the need for isolating the rearrangement products. From a practicality perspective, this work demonstrates a mechanochemical synthesis of chiral vicinal diamines that can be readily adapted in academic laboratories and, potentially, in industrial settings.

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“…Similarly, modulating reactivity using external forces need not be constrained by IRC-based rules and can involve pathways that utilize higher-index saddles. Thus, in mechanochemistry [ 17 , 18 , 19 , 20 , 21 ], the energetics of the various index saddles alone is no longer a useful criterion and it is quite feasible for the “forced” dynamics to prefer pathways that explore the various high-index saddle regions.…”

Section: Introductionmentioning

confidence: 99%

Classical and Quantum Dynamical Manifestations of Index-$$2$$ Saddles: Concerted Versus Sequential Reaction Mechanisms

2021

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The presence of higher-index saddles on a multidimensional potential energy surface is usually assumed to be of little significance in chemical reaction dynamics. Such a viewpoint requires careful reconsideration, thanks to elegant experiments and novel theoretical approaches that have come about in recent years. In this work, we perform a detailed classical and quantum dynamical study of a model two-degree-of-freedom Hamiltonian, which captures the essence of the debate regarding the dominance of a concerted or a stepwise reaction mechanism. We show that the ultrafast shift of the mechanism from a concerted to a stepwise one is essentially a classical dynamical effect. In addition, due to the classical phase space being a mixture of regular and chaotic dynamics, it is possible to have a rich variety of dynamical behavior, including a Murrell – Laidler type mechanism, even at energies sufficiently above that of the index- saddle. We rationalize the dynamical results using an explicit construction of the classical invariant manifolds in the phase space. Supplementary Information The online version contains supplementary material with details on computation of the invariant manifolds which available at 10.1134/S1560354721020052.

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Force-Induced Dissolution of Imaginary Mode in Mechanochemical Reaction: Dibenzophenazine Synthesis

Cited by 11 publications

References 64 publications

Tribochemistry, Mechanical Alloying, Mechanochemistry: What is in a Name?

Tribochemistry, Mechanical Alloying, Mechanochemistry: What is in a Name?

Solvent-Free Mechanochemical Diaza-Cope Rearrangement

Classical and Quantum Dynamical Manifestations of Index-$$2$$ Saddles: Concerted Versus Sequential Reaction Mechanisms

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