Semiempirical studies on the transition structure of the Baeyer and Villiger rearrangement. The reaction of acetone with alkyl and aryl peracids

Cadenas, Raúl A.; Reyes, Lino; Lagúnez-Otero, Jaime; Cetina, R.

doi:10.1016/s0166-1280(99)00329-2

Cited by 24 publications

(23 citation statements)

References 25 publications

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“…Several computational studies of the BV mechanism have been published in which concerted transition states (TS) have been modelled assuming a neutral mechanism in non-polar solvents. 15,16,[20][21][22][23][24][25][26][27][28][29][30][31][32] The complete mechanism, including the Brønsted acid catalysis on the addition and migration steps, has been modelled only by Okuno, 15 Grein et al, 20 and our group. 32 Strong evidence for a neutral and concerted mechanism was recently shown for the BV reactions of propanone and cyclohexanone with trifluoroperacetic acid, catalyzed by trifluoroacetic acid Fig.…”

Section: Introductionmentioning

confidence: 99%

The Baeyer–Villiger reaction: solvent effects on reaction mechanisms

2009

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This study focuses on the Baeyer-Villiger reaction of propanone and performic acid, with formic acid as catalyst. Continuum solvation methods (EIF-PCM and CPCM) and two density functionals (B3LYP and MPWB1K) are used to study solvent effects on two types of reaction mechanisms: concerted non-ionic and stepwise ionic. The ionic mechanism is the one found in most organic chemistry textbooks; it begins with the protonation of the ketone by the acid catalyst, even though this reaction normally takes place in non-polar solvents such as dichloromethane. Our calculations show that the concerted non-ionic pathway, which is the least energetic in non-polar solvents such as dichloromethane, becomes more energetic the more polar the solvent. After investigating a variety of non-ionic and ionic pathways in water, it is found that the addition step seems to be ionic but the migration step, which is rate-determining, is uncatalyzed, non-ionic and fully concerted. These results confirm the experimental findings in solvents of low to medium polarity that the rate constant of the reaction decreases as the solvent polarity increases. Moreover, we find that contrary to what is commonly accepted, in the addition and migration ionic steps the deprotonation of the ionic species occurs in a concerted manner with the other chemical events taking place.

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Section: Introductionmentioning

confidence: 99%

The Baeyer–Villiger reaction: solvent effects on reaction mechanisms

2009

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“…11 In our first study of this reaction using a simple model (performic acid and acetone), 22 we showed that the transitionstate (TS) geometry associated with the BV rearrangement and the general orientation of the transition vectors are nearly invariant of the calculation method. More recently, 23 we used this finding to analyze the migration step on the BV reaction of acetone with some alkyl and aryl peracids by using AM1 and PM3 methods. To the best of our knowledge, there has not been a computational systematic study of the effect of both donor and acceptor substituents at every position of the migrating aryl group on the rates of the substrates in the BV reaction.…”

Section: Introductionmentioning

confidence: 99%

Substituent Effects in the Migration Step of the Baeyer−Villiger Rearrangement. A Theoretical Study

et al. 2005

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Quantum mechanical calculations have been performed on the migration step of the Baeyer-Villiger (BV) rearrangements of some acetophenones, p-RC6H4COCH3 (R = CN, Cl, H, CH3, CH3O) with m-chloroperbenzoic acid. The energy barriers, charge distributions, and frontier molecular orbitals determined for the aryl migration step explain the effects of substituents on the reactivity of these ketones. A plot of the log of relative oxidation rates of the ketones versus their corresponding calculated energy barriers of the migration stage showed a downward deviation for the p-OCH3 derivative. This result is consistent with a change in the rate-determining step, from the aryl migration to the carbonyl addition, in the case of p-methoxyacetophenone, according to the suggestion that the rate-determining step of the BV oxidation can change with variations in the substituent group.

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“…All MD simulations were performed using the Amber 18 molecular dynamics program with the parm99SB [14] and GAFF force fields [21]. The structures were placed within an octahedral box of TIP3P waters [22,23] and counter ions were added to make the entire system neutral. The systems were subjected to two initial energy minimizations and to 500 ps of equilibration in a NVT ensemble using Langevin dynamics with small restraints on the protein (10 kcal/mol) to heat the system from 0 to 300 K. Production simulations were carried out at 300 K in the NPT ensemble using Langevin dynamics with a collision frequency of 1.0 ps −1 .…”

Section: Molecular Dynamics (Md) Simulationsmentioning

confidence: 99%

SLMP53-1 interacts with wild-type and mutant p53 DNA-binding domain and reactivates multiple hotspot mutations

Gomes

Ramos

Gomes

et al. 2020

Biochimica et Biophysica Acta (BBA) - General Subjects

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Background: Half of human cancers harbour TP53 mutations that render p53 inactive as a tumor suppressor. As such, reactivation of mutant (mut)p53 through restoration of wild-type (wt)-like function represents one of the most promising therapeutic strategies in cancer treatment. Recently, we have reported the (S)-tryptophanolderived oxazoloisoindolinone SLMP53-1 as a new reactivator of wt and mutp53 R280K with in vitro and in vivo p53-dependent antitumor activity. The present work aimed a mechanistic elucidation of mutp53 reactivation by SLMP53-1. Methods and results: By cellular thermal shift assay (CETSA), it is shown that SLMP53-1 induces wt and mutp53 R280K thermal stabilization, which is indicative of intermolecular interactions with these proteins. Accordingly, in silico studies of wt and mutp53 R280K DNA-binding domain with SLMP53-1 unveiled that the compound binds at the interface of the p53 homodimer with the DNA minor groove. Additionally, using yeast and p53-null tumor cells ectopically expressing distinct highly prevalent mutp53, the ability of SLMP53-1 to reactivate multiple mutp53 is evidenced. Conclusions: SLMP53-1 is a p53-activating agent with the ability to directly target wt and a set of hotspot mutp53. General Significance: This work reinforces the encouraging application of SLMP53-1 in the personalized treatment of cancer patients harboring distinct p53 status.

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Semiempirical studies on the transition structure of the Baeyer and Villiger rearrangement. The reaction of acetone with alkyl and aryl peracids

Cited by 24 publications

References 25 publications

The Baeyer–Villiger reaction: solvent effects on reaction mechanisms

The Baeyer–Villiger reaction: solvent effects on reaction mechanisms

Substituent Effects in the Migration Step of the Baeyer−Villiger Rearrangement. A Theoretical Study

SLMP53-1 interacts with wild-type and mutant p53 DNA-binding domain and reactivates multiple hotspot mutations

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