Mechanism(s) of thermal decomposition of N-Nitrosoamides: A density functional theory study

Brea, Oriana; Daver, Henrik; Rebek, Julius; Himo, Fahmi

doi:10.1016/j.tet.2018.12.054

Cited by 10 publications

(13 citation statements)

References 51 publications

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“…The calculations nicely reproduced the inhibition of the decomposition inside the capsule (Brea et al ., 2019 a , 2019 b ). They confirm that the inhibition is due to an increase in the energy barrier of the 1,3 N → O acyl transfer to form the diazoester intermediate, which is the rate-determining step of the reaction.…”

Section: Rearrangementmentioning

confidence: 99%

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Confined molecules: experiment meets theory in small spaces

Rebek

2020

Quart. Rev. Biophys.

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The behavior of molecules confined to small spaces is fascinating chemistry and lies at the heart of signaling processes in biology. Our approach to confinement is through reversible encapsulation of small molecules in synthetic containers. We show that confinement leads to amplified reactivities in bimolecular reactions, stabilization of otherwise reactive species, and limitation in motions that create new stereochemical arrangements. The isolation of molecules from solvent makes for manageable computations and has stimulated theorist to examine reaction details in the limited space. Transition states for reactions and rearrangements can be calculated, the effects of (de)solvation can be evaluated and the magnetic properties of the containers can be compared with experimental observations. Finally, we outline several potential applications, including entanglement chemistry and the use of isomers in data storage.

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Section: Rearrangementmentioning

confidence: 99%

“…That is, confinement favors (hypothetical) intermediates that might form inside the capsule but are unexpected in solution. The details of the reaction outside were thoroughly examined by density-functional theory (DFT) calculations (Brea et al ., 2019 a , 2019 b ).…”

Section: Rearrangementmentioning

confidence: 99%

Confined molecules: experiment meets theory in small spaces

Rebek

2020

Quart. Rev. Biophys.

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“…We have very recently used density functional theory (DFT) calculations to investigate the full reaction mechanism of the thermal decomposition of N -nitrosoamides, employing both aliphatic and aromatic substrates in two different solvents, mesitylene and methanol . The obtained mechanisms in mesitylene are shown in Scheme and the associated energy profiles are given in the Supporting Information.…”

Section: Introductionmentioning

confidence: 99%

“…Several pathways were evaluated computationally for the formation of N 2 and 3 from 4 , all of which turned out to start with the isomerization of 4 around the NN double bond to give 4′ via a cleavage–recombination transition state ( 4′-TS in Scheme ). The following steps of the reaction were found to depend on the nature of the substituent group. For aliphatic diazoesters, the products are obtained through the intermediates carboxylic acid 5 and diazo compound 6 , which are formed by an α-elimination reaction ( 5-TS ).…”

Section: Introductionmentioning

confidence: 99%

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Modeling Decomposition of N-Nitrosoamides in a Self-Assembled Capsule

et al. 2019

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Density functional theory calculations are employed to investigate the mechanism and energies of the decomposition of N-nitrosoamides in the presence of a resorcinarene-based self-assembled nanocapsule. From experiments, it is known that confinement in the capsule inhibits the thermal decomposition of these compounds. N-Nitrosoamides with both aromatic and aliphatic substituents are considered here and the calculations show that, for both kinds, binding to the capsule leads to a significant increase in the energy barrier of the rate-determining step, the 1,3 N→O acyl transfer reaction. A distortion−interaction analysis is conducted to probe the reasons behind the inhibition of the reaction. In addition, we characterized hypothetical intermediates that might be involved in the formation of the decomposition products inside the capsule. Interestingly, it is found that the capsule stabilizes ion-pair species that are unstable in mesitylene solution. Finally, a possible explanation is proposed for the observed encapsulation of the decomposition product of only one of the substrates.

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