Journal of Physical Organic Chemistry最新文献

{"title":"Computational Study of the Formation of α and β O-Unsaturated Glycosides via Ferrier Rearrangement","authors":"Yuri Antonio Fortunato da Silva,&nbsp;Cristiano Costa Bastos,&nbsp;João Rufino de Freitas Filho","doi":"10.1002/poc.70041","DOIUrl":"https://doi.org/10.1002/poc.70041","url":null,"abstract":"<p>We studied the formation of new 2,3-unsaturated <i>O</i>-glycosides via Ferrier rearrangement using electronic structure calculations at the B3LYP/6-31g level. Using the Gibbs free energy variation, it was possible to indicate the formation of an intermediate stabilized by the anchimeric assistance at C3, which explains the preferred formation of the α-anomer. The calculations show that there is also the possibility of the formation of an anchimeric assistance intermediate at C4, which also favors the formation of the intermediate at C3. We analyzed the hypothesis of the repulsion of the aglycone with the acetoxy group at C6, and the results showed that there is less repulsion from the top of the oxonium ion, which corroborates the thermodynamic data. We propose a transition state starting from the C3 intermediate that explains the formation of the alpha anomer. The effect of the hyperconjugation present in the anomeric effect was studied using the NBO model, and according to the calculations compared to the literature, this factor did not prove to play a fundamental role in explaining the preferential formation of the α-anomer. Thus, the main factor favoring the preferential formation of the α-anomer is the spontaneous formation of the intermediate at C3, which prevents the formation of the β-anomer.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 11","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70041","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145224044","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Computational Review for Substituent Effect on the Fused Pyrrole Remote Hammick N-Heterocyclic Germylenes (RHNHGes) via the Adsorption Process to NCBC17 Heterofullerenic Isomers, at DFT","authors":"Farnaz Behmagham,&nbsp;Hassan Valizadeh,&nbsp;Esmail Vessally,&nbsp;Rovnag Rzayev,&nbsp;Subbulakshmi Ganesan,&nbsp;Mayank Kundlas","doi":"10.1002/poc.70031","DOIUrl":"https://doi.org/10.1002/poc.70031","url":null,"abstract":"&lt;div&gt;\u0000 \u0000 &lt;p&gt;This study presents a comprehensive density functional theory (DFT) investigation into the substituent effects on the fused pyrrole remote Hammick &lt;i&gt;N&lt;/i&gt;-heterocyclic germylenes (RHNHGes), focusing on their singlet and triplet states and their interactions with NCBC&lt;sub&gt;17&lt;/sub&gt; heterofullerenic isomers. The research examines a series of benzogermapyridine-4-ylidene derivatives (&lt;b&gt;I&lt;/b&gt;&lt;sub&gt;&lt;b&gt;s&lt;/b&gt;&lt;/sub&gt; and &lt;b&gt;I&lt;/b&gt;&lt;sub&gt;&lt;b&gt;t&lt;/b&gt;&lt;/sub&gt;) and fused furan analogues (&lt;b&gt;II&lt;/b&gt;&lt;sub&gt;&lt;b&gt;X-s&lt;/b&gt;&lt;/sub&gt;, and &lt;b&gt;II&lt;/b&gt;&lt;sub&gt;&lt;b&gt;X-t&lt;/b&gt;&lt;/sub&gt;, X = CH&lt;sub&gt;2&lt;/sub&gt;, SiH&lt;sub&gt;2&lt;/sub&gt;, GeH&lt;sub&gt;2&lt;/sub&gt;, NH, PH, AsH, O, S, and Se), evaluating their thermodynamic and kinetic stability, electronic properties, and reactivity descriptors. The greatest stabilization is supported by the NH substituent, and the least stabilization is provided by Se in terms of singlet-triplet energy differences (Δ&lt;i&gt;E&lt;/i&gt;&lt;sub&gt;s-t&lt;/sub&gt; = &lt;i&gt;E&lt;/i&gt;&lt;sub&gt;t&lt;/sub&gt;&lt;i&gt;–E&lt;/i&gt;&lt;sub&gt;s&lt;/sub&gt;) exhibiting the highest Δ&lt;i&gt;E&lt;/i&gt;&lt;sub&gt;s-t&lt;/sub&gt; of 57.78 kcal/mol and the lowest Δ&lt;i&gt;E&lt;/i&gt;&lt;sub&gt;s-t&lt;/sub&gt; of 46.60 kcal/mol, correspondingly, and suggesting singlet &lt;b&gt;II&lt;/b&gt;&lt;sub&gt;&lt;b&gt;NH&lt;/b&gt;&lt;/sub&gt; and &lt;b&gt;II&lt;/b&gt;&lt;sub&gt;&lt;b&gt;Se&lt;/b&gt;&lt;/sub&gt; as the most and least stable species. All singlet RHNHGes are established as ground state (GS) with positive Δ&lt;i&gt;E&lt;/i&gt;&lt;sub&gt;s-t&lt;/sub&gt;, higher band gaps, and greater thermodynamic and kinetic stability compared to their triplet counterparts. In addition, singlet &lt;b&gt;II&lt;/b&gt;&lt;sub&gt;&lt;b&gt;NH&lt;/b&gt;&lt;/sub&gt; and &lt;b&gt;II&lt;/b&gt;&lt;sub&gt;&lt;b&gt;Se&lt;/b&gt;&lt;/sub&gt; are demonstrated the polarity of 1.78 and 2.78 Debye; polarizability of 114.68 and 130.50 &lt;i&gt;a.u&lt;/i&gt;.; and the smallest vibrational frequency (υ&lt;sub&gt;min&lt;/sub&gt;) of 229.19 and 182.97 cm&lt;sup&gt;−1&lt;/sup&gt;, respectively. Nemirowski and Schreiner realized that the classical π-donor/σ-acceptor amino substituent simultaneously stabilizes singlet NHCs and destabilizes the corresponding triplet ones. In contrast to this statement, in this work, all substituents were stabilized not only singlet RHNHGes but also triplet RHNHGes. Substituent effects are rationalized by electronegativity and π-electron delocalization involving the germanic center (GC), mediated through inductive and mesomeric effects. The detailed analyses reveal that the singlet RHNHGes possess more charge, lower nucleophilicity, higher electrophilicity, more chemical potential, more hardness, and less softness than its triplet state. Stabilization is anticipated dependent on the substituent's electronegativity in the fused pyrrole ring and π-electron delocalization with the empty 4p-orbital of the GC through either inductive effect or mesomeric effect. Adsorption studies with NCBC&lt;sub&gt;17&lt;/sub&gt; heterofullerenic isomers further elucidate how substituent identity modulates RHNHGe stability and interaction energies. These findings provide valuable insights into the design and stabilization of novel divalent germylene species, with implications for their reactivity and potential applications in or","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 11","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145111284","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Kinetics and Mechanism of the Antioxidant Action of Phenothiazine and Its Derivatives in the Radical Chain Oxidation Reaction of Isopropyl Alcohol","authors":"K. S. Sharaeva,&nbsp;G. M. Shaymordanova,&nbsp;I. V. Safarova,&nbsp;E. F. Safarov,&nbsp;A. Ya. Gerchikov,&nbsp;Yu. S. Zimin,&nbsp;D. A. Nedopekina,&nbsp;A. Yu Spivak","doi":"10.1002/poc.70038","DOIUrl":"https://doi.org/10.1002/poc.70038","url":null,"abstract":"<div>\u0000 \u0000 <p>A series of biologically active phenothiazine derivatives were studied as inhibitors of the free-radical chain oxidation of isopropyl alcohol by atmospheric oxygen. It was found that these compounds exhibit antioxidant properties, effectively suppressing the oxidation process. The key rate constants quantitatively characterizing the efficiency of their antioxidant action were determined. Mathematical modeling was used to analyze the proposed oxidation mechanism, identifying the critical stages that determine the inhibitory efficacy of phenothiazines. It was shown that the inhibitor regeneration reaction plays a significant role, leading to a high inhibition capacity. The application of mathematical modeling allowed the proposal of an oxidation mechanism that provides a comprehensive explanation for all currently available experimental and literature data.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 10","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145038089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Aromaticity and Photoreactivity of 4- and 3-Nitrenopyridine 1-Oxides and Phenylnitrene","authors":"Fiona J. Wasson,&nbsp;Anindya Borah,&nbsp;Dmitrii Govorov,&nbsp;W. Dinindu Mendis,&nbsp;James S. Poole,&nbsp;Bruce S. Ault,&nbsp;William L. Karney,&nbsp;Anna D. Gudmundsdottir","doi":"10.1002/poc.70035","DOIUrl":"https://doi.org/10.1002/poc.70035","url":null,"abstract":"<p>The pursuit of sustainable organic synthesis has renewed interest in photochemistry, as sunlight-driven reactions provide eco-friendly alternative methods. Although the relationships among structure, properties, and reactivity are well established for ground-state molecules, the understanding of excited states and reactive intermediates, such as triplet and singlet arylnitrenes, remains limited. Herein, we investigated the properties of triplet and singlet 4-nitrenopyridine-1-pyridine oxide (<b>1N</b>), 3-nitrenopyridine-1-pyridine oxide (<b>2N</b>), and phenylnitrene (<b>PhN</b>) using density functional theory (DFT), complete active space self-consistent field (CASSCF(10,9)), and complete active space second-order perturbation theory (CASPT2(10,9)) calculations. Bond length analysis demonstrated that ³<b>1N</b> and ¹<b>1N</b>, as well as ¹<b>2N</b> and ¹<b>PhN</b>, exhibit significant imine biradical character, whereas the structures of ³<b>2N</b> and ³<b>PhN</b> are better described as benzene-like. Nucleus-independent chemical shift (NICS(0), NICS(1.7)_ZZ) and anisotropy of induced current density (ACID) calculations were performed to compare the induced magnetic currents in these molecules. These analyses demonstrated that ³<b>1N</b> is weakly aromatic, whereas ³<b>2N</b> and ³<b>PhN</b> are best described as having Baird aromaticity. In contrast, singlet nitrenes ¹<b>1N</b>, ¹<b>2N</b>, and ¹<b>PhN</b> are nonaromatic. In addition, irradiation of <b>1</b> in argon matrices verified that ³<b>1N</b> reacts photochemically to form corresponding ketenimine <b>1K</b>. Finally, the absorption difference spectrum of ³<b>1N</b> in a frozen 2-methyltetrahydrofuran (mTHF) matrix exhibited resolved vibrational structure, suggesting the vibrational coupling to another electronic state. These insights into the structure and aromaticity of heterocyclic nitrenes could provide new avenues for modulating the reactivity of triplet ground state and triplet excited molecules.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 10","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70035","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144998940","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Intermolecular Dynamics of Aniline in Ethyl Acetate: A Raman Spectroscopy and DFT Approach","authors":"Abduvakhid Jumabaev,&nbsp;Bekzod Khudaykulov,&nbsp;Hakim Hushvaktov,&nbsp;Utkirjon Holikulov,&nbsp;Iryna Doroshenko,&nbsp;Ahmad Absanov,&nbsp;Naveen Kosar,&nbsp;Tariq Mahmood","doi":"10.1002/poc.70039","DOIUrl":"https://doi.org/10.1002/poc.70039","url":null,"abstract":"<div>\u0000 \u0000 <p>The intermolecular interactions between aniline (PhNH₂) and ethyl acetate (EtOAc) were investigated by using Raman spectroscopy and density functional theory (DFT) calculations. Experimental Raman spectra revealed red and blue shifts in the vibrational bands of PhNH₂, indicating the presence of weak hydrogen bonding and van der Waals interactions with EtOAc. A prominent hydrogen bonding was observed between the NH₂ group of PhNH₂ and the carbonyl (C=O) group of EtOAc. DFT calculations were performed to support the experimental findings, showing strong agreement. Molecular electrostatic potential (MEP) maps highlighted the electrophilic nature of the NH₂ group and the nucleophilic character of the C=O group, corroborating the observed hydrogen bonding. Frontier molecular orbital (FMO) analysis revealed that the HOMO–LUMO energy gap of PhNH₂···(EtOAc)_n (<i>n</i> = 1–3) complexes decreases with increasing number of EtOAc molecules, reaching a minimum of 4.69 eV. Quantum theory of atoms in molecules (QTAIM) analysis confirmed that the complexation is primarily governed by weak hydrogen bonding and van der Waals interactions involving N-H···O=C, H-N···H–C, and C-H···O=C contacts. This study provides valuable insights into solvent effects on the molecular behavior of aniline, with implications for both fundamental research and practical applications in physics and chemistry.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 10","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144998858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Effects of Substituents on the Stabilities of Bridgehead Radicals","authors":"Gary W. Breton","doi":"10.1002/poc.70036","DOIUrl":"https://doi.org/10.1002/poc.70036","url":null,"abstract":"<div>\u0000 \u0000 <p>The relative stabilities of unsubstituted bicyclic bridgehead radicals have been previously shown to be dependent primarily upon differences in strain energies between the radicals and the corresponding saturated compounds. Although substituents are known to strongly affect the stability of acyclic carbon-based radicals, the effect of replacing at least one of the one-carbon bridges of bicyclic bridgehead radicals with a substituent was unknown. Because of geometrical constraints imposed by the bicyclic frameworks, the bridging substituents are unable to adopt conformations that optimize their stabilizing effects. Using [2.2.1] substituted derivatives as models, we have shown that substituents exert their effects via two primary modes. First, the presence of substituents influences the extent of hyperconjugative interactions between the SOMO and properly aligned bonds as revealed by NBO calculations. Second, when the substituents are frozen into a geometry reflective of that in the bicyclic radicals, they exert a direct impact upon the radical site that can be very different from that in the corresponding acyclic compounds. Neither of these effects alone rationalizes the relative stabilities of the radicals with various substituents. However, when combined, they offer a reasonable correlation with the observed relative energies. Generally, the effect of substituents on other bicyclic frameworks appears to follow a regular pattern of stabilization versus destabilization. The effect of changing the size of the bicyclic framework while maintaining the same substituent was also investigated. Generally, the order of relative energies mirrored that of the unsubstituted all-carbon analogs, suggesting that strain remains the primary factor in determining stability.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 10","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144935216","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Halochromism of Phenol Red in Aqueous Solution: A Comparative Theoretical Analysis of Excitations of Dianion and Anion","authors":"Victor Kostjukov","doi":"10.1002/poc.70037","DOIUrl":"https://doi.org/10.1002/poc.70037","url":null,"abstract":"<div>\u0000 \u0000 <p>MN15/6-31++G(d,p)/IEFPCM theory level gave a good agreement between the calculated vibronic and experimental absorption spectra of the dianion, in both the maximum position and the shape. Vibronic transitions of the dianion activate only two motions in the S₁ state, namely, torsional vibrations of two aromatic rings (A and B) and the SO₃ group attached to the third ring. Significant photoinduced distortions of the spatial structure of the anion (A and B rings, being almost parallel to each other in the ground state, become mutually perpendicular in the excited state) led to a failure of the Franck-Condon computational procedure for calculating its vibronic spectrum. Photo-induced shifts of the electron density are analyzed. The ring with the SO₃ group attached is not involved in these charge redistributions for both the dianion and the anion. The negative solvatochromism of the dianion and the positive one of the anion observed experimentally were explained both from the point of view of non-specific dipole–dipole interactions with the solvent (changes in the dipole moments of the solutes upon excitation) and specific ones (strengthening/weakening of strong hydrogen bonds of the dianion and anion with water molecules).</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 10","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144927371","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Theoretical Comparative Study on Thermal Stabilities of Ammonium Pentazolate and Its Cocrystals","authors":"Shuaijie Jiang,&nbsp;Yuangang Xu,&nbsp;Qiuhan Lin,&nbsp;Pengcheng Wang,&nbsp;Ming Lu","doi":"10.1002/poc.70033","DOIUrl":"https://doi.org/10.1002/poc.70033","url":null,"abstract":"<div>\u0000 \u0000 <p>Pentazolate compounds have garnered considerable interest as promising building blocks for novel polynitrogen compounds. Leveraging insights from the study of other energetic materials, researchers have enhanced the thermal stability of pentazolate compounds by synthesizing cocrystals, thereby addressing the issue of their poor thermal stability. In this study, the thermal decomposition mechanism of NH₄N₅ and its cocrystals ((N₅)₆(H₃O)₃(NH₄)₄Cl and NH₄N₅·1/6NH₄Cl) was investigated from a theoretical perspective. Laplace bond orders, decomposition pathways, transition states, interaction energies, and aromaticity were employed in the analysis. The computational results indicate that the asymmetric structure <b>R3</b> of NH₄N₅·1/6NH₄Cl demonstrated incredible thermal stability and aromaticity, with a minimum Laplacian bond order of 1.036, a decomposition barrier of 29.48 kcal mol⁻¹, and an ELF-π value of 0.719. Therefore, co-crystallization with high-energy materials with high decomposition temperatures can enhance the thermal stability of pentazolate compounds.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 9","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144773639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Study on the Aromaticity of [n]Circulene (n = 3–8)","authors":"Satewaerdi Helili,&nbsp;Ablikim Kerim","doi":"10.1002/poc.70032","DOIUrl":"https://doi.org/10.1002/poc.70032","url":null,"abstract":"<div>\u0000 \u0000 <p>The topological resonance energy method was employed to analyze [<i>n</i>]circulene systems (<i>n</i> = 3–8) and predict their aromaticity. Calculations revealed that all compounds exhibit some aromatic properties. Local aromaticity of each ring was assessed using bond resonance energy (BRE), circuit resonance energy, and magnetically based superaromatic stabilization energy (<i>m</i>-SSE) indices. Our results indicate that the BRE method overestimates the degree of local aromaticity in the central ring. The local aromaticity, as determined by the <i>m</i>-SSE index, has been compared with other ring indices reported in the literature. Additionally, the Hückel–London ring current model was used to study aromaticity, showing that molecular perimeters sustain diamagnetic bond currents, whereas central rings sustain paramagnetic bond currents. For the individual rings, both the energetic and magnetic criteria of aromaticity predict similar trends in the magnitude of local aromatic and antiaromatic states.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 9","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144725719","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical Study on the Prooxidant Activity of α- and β-Lapachones in Aqueous Media","authors":"Mario A. Vera-Guzmán,&nbsp;Ángel Trigos,&nbsp;Alberto V. Jerezano,&nbsp;Manuel E. Medina","doi":"10.1002/poc.70030","DOIUrl":"https://doi.org/10.1002/poc.70030","url":null,"abstract":"<div>\u0000 \u0000 <p>The prooxidant activities of α- and β-lapachones were studied in aqueous media using density functional theory. Although these compounds are well-known prooxidants and have applications as alternatives in the treatment of tumor cells, little is known about the reaction mechanisms involved. The prooxidant activity of α- and β-lapachones considered their reduced forms; they are hydronaphthoquinones <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mi>H</mi>\u0000 <mn>2</mn>\u0000 </msub>\u0000 <msub>\u0000 <mi>Q</mi>\u0000 <mi>α</mi>\u0000 </msub>\u0000 </mrow>\u0000 <annotation>$$ {mathrm{H}}_2{mathrm{Q}}_{alpha } $$</annotation>\u0000 </semantics></math> and <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mi>H</mi>\u0000 <mn>2</mn>\u0000 </msub>\u0000 <msub>\u0000 <mi>Q</mi>\u0000 <mi>β</mi>\u0000 </msub>\u0000 </mrow>\u0000 <annotation>$$ {mathrm{H}}_2{mathrm{Q}}_{beta } $$</annotation>\u0000 </semantics></math>, whereas the single electron transfer mechanism was considered in the reduction reaction where oxygen, hydrogen peroxide, copper, and iron were substrates. Two reaction routes were identified for the prooxidant activities of H₂Q_α and H₂Q_β: The first considered that the metals were not present in the reduction reactions of oxygen and hydrogen peroxide and obtained reaction rates of 10⁶–10⁷ M⁻¹ s⁻¹; the second considered that the metals copper and iron were present in the reduction reactions and the reaction rates were limited by diffusion. Understanding the reaction mechanism involved in the prooxidant activity of α- and β-lapachones and the physiological importance of these molecules could be employed to comprehend the anticancer properties of compounds in which prooxidant activity is involved.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 9","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144687861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}