Journal of Physical Organic Chemistry最新文献

Mechanism and Diastereoselectivity of the Photo-/NHC Cocatalyzed Fluoroacylation of Benzofurans: A Theoretical View

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-03-12 DOI: 10.1002/poc.70007

Zehua Li, Jiying Liu, Jiabin Liu, Panpan Bao, Huixian Jing, Hui Chen, Wenjing Zhang

{"title":"Mechanism and Diastereoselectivity of the Photo-/NHC Cocatalyzed Fluoroacylation of Benzofurans: A Theoretical View","authors":"Zehua Li, Jiying Liu, Jiabin Liu, Panpan Bao, Huixian Jing, Hui Chen, Wenjing Zhang","doi":"10.1002/poc.70007","DOIUrl":"https://doi.org/10.1002/poc.70007","url":null,"abstract":"<div>\u0000 \u0000 <p>The NHC/photoredox cocatalysis proposes an alternative to conventional methods for acylation of the unsaturated bonds. But it is still a great challenge to effectively control the stereoselectivities stemming from couplings of the ketyl radicals and the alkyl radicals. In this work, we have selected the photo-/NHC cocatalyzed fluoroaroylation of benzofurans as the computational model for density functional theory (DFT) studies, intending to unveil mechanisms of the fluorine-induced diastereoselectivities and thus to provide guidance to future rational design of promising catalytic reactions with high stereoselectivities. The computational results reveal that a fluorine-bearing zwitterion intermediate is yielded after nucleophilic addition of the NHC catalyst to the acyl fluorides, because fluorine anion is a poor leaving group. The cross-coupling of the ketyl radical and the tertiary carbon radical is the diastereoselectivity-determining step, and the configuration with the bulky NHC-stabilized ketyl radical bonded <i>trans</i> to the α-fluorine substitution is energetically favor over that giving the <i>cis</i> configuration. The distortion–interaction energy calculations combined with the geometry analysis indicate that the repulsion of the α-fluorine atom on the neighboring carbon results in significant distortions of the two coupling partners in the <i>cis</i>-configuration transition state and therefore leads to high diastereoselectivities. In addition, it is unveiled that the nucleophilicity of the carbene atom could be substantially influenced by electron delocalization. Moreover, the steric hindrance arose from the N(2)-phenyl group warrants attention as it may reduce remarkable geometry distortions with approach of the acyl fluoride compound.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 4","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143612576","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}

引用次数: 0

Citrate-Based Ionic Liquids for CO2 Capture—A Computational Approach Toward Environmentally Benign Ionic Liquid Anions

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-03-04 DOI: 10.1002/poc.70009

Uttama Mukherjee

{"title":"Citrate-Based Ionic Liquids for CO2 Capture—A Computational Approach Toward Environmentally Benign Ionic Liquid Anions","authors":"Uttama Mukherjee","doi":"10.1002/poc.70009","DOIUrl":"https://doi.org/10.1002/poc.70009","url":null,"abstract":"<div>\u0000 \u0000 <p>This work aims to explore and characterize citrate as an anion of nontoxic and biocompatible origin, which is a crucial step to developing a sustainable CO<sub>2</sub> capture process through ionic liquids (ILs). Citrate ILs have recently been synthesized and utilized as solvents and catalysts for various synthetic purposes in the industry. These are found to be easily recycled, nonpolluting, less corrosive, and easy to synthesize. In this work, citrate–CO<sub>2</sub> and citrate–bmim (1-butyl-3-methylimidazolium) ion pair (IP)–CO<sub>2</sub> interactions have been theoretically explored via carboxylation reactions and various electronic structure calculations. The results indicate favorable citrate–CO<sub>2</sub> interactions in the gas as well as the aqueous phase resulting in monocarboxylates, dicarboxylates, and tricarboxylates of citrates owing to the availability of its three carboxylate O atoms. Even as citrate is paired with bmim, it shows the possibility of multiple site CO<sub>2</sub> absorptions. This system should thus serve as a pathway for enhanced CO<sub>2</sub> capture and better desorption by reducing the formation of carbene–CO<sub>2</sub> complex (reduced basicity of the anion and enhanced steric hindrance of the cation). The study reveals that in the IP, at least one of the citrate O atoms can form a covalent carboxylate (chemisorption) with CO<sub>2</sub> while other available O sites may weakly bind CO<sub>2</sub> (physisorption).</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 4","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143554656","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}

引用次数: 0

Unexpected the Mechanistic Pathway of the Hydrogen Evolution Reaction in the Presence of N-Substituted Hydro-Derivatives of Ortho-Bipyridines

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-28 DOI: 10.1002/poc.70010

A. V. Dolganov, A. D. Yudina, L. A. Klimaeva, O. Yu. Ganz, Yu. V. Ulyakina, A. A. Burmistrova, T. O. Karpunina, A. A. Kuzmicheva, S. G. Kostryukov

{"title":"Unexpected the Mechanistic Pathway of the Hydrogen Evolution Reaction in the Presence of N-Substituted Hydro-Derivatives of Ortho-Bipyridines","authors":"A. V. Dolganov, A. D. Yudina, L. A. Klimaeva, O. Yu. Ganz, Yu. V. Ulyakina, A. A. Burmistrova, T. O. Karpunina, A. A. Kuzmicheva, S. G. Kostryukov","doi":"10.1002/poc.70010","DOIUrl":"https://doi.org/10.1002/poc.70010","url":null,"abstract":"<div>\u0000 \u0000 <p>Using cyclic voltammetry, the electrochemical properties and electrocatalytic activity in the reaction of molecular hydrogen formation in the presence of 2,2′-bipyridinium-1,1′-diium and 2,2′-bipyridinium-1-ium perchlorates were studied. The electrochemical reduction product of 2,2′-bipyridinium-1,1′-diium perchlorate decomposes to form molecular hydrogen, but in the case of 2,2′-bipyridinium-1-ium perchlorate, a two-electron reduction product is formed −(E)-1H,1′H-2,2′-bipyridinylidene. It has been shown that the hydrogen evolution reaction (HER) in the presence of 2,2′-bipyridinium-1,1′-diium and 2,2′-bipyridinium-1-ium perchlorates occurs at the same potentials but through different mechanisms. In both cases, the potential is −0.85 V according to the CECE mechanism, but at a potential of −1.25 V according to the ECEC mechanism. In both cases, the key intermediate, through which both mechanisms are realized, is (E)-1H,1′H-2,2′-bipyridinylidene.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 4","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143521828","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}

引用次数: 0

The Importance of Strain on the Relative Energies of Bridgehead Radicals 应变对桥头自由基相对能量的重要性

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-21 DOI: 10.1002/poc.70004

Gary W. Breton

引用次数: 0

The Position of ‘Proton Transfer’ Phenomena in Case of Fluoride Detection: A Minireview

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-18 DOI: 10.1002/poc.70008

Atanu Mahata, Arabinda Mallick

引用次数: 0

A Computational Prediction: Enhancing Visible Light Harvesting Through Minor Modification of Donor Moiety in Triphenylamine-Based Dyes for DSSCs

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-18 DOI: 10.1002/poc.70005

Morad M. El-Hendawy, Samar T. Hassan, Emad E. El-Katori, Mahmoud M. A. Mohamed

{"title":"A Computational Prediction: Enhancing Visible Light Harvesting Through Minor Modification of Donor Moiety in Triphenylamine-Based Dyes for DSSCs","authors":"Morad M. El-Hendawy, Samar T. Hassan, Emad E. El-Katori, Mahmoud M. A. Mohamed","doi":"10.1002/poc.70005","DOIUrl":"https://doi.org/10.1002/poc.70005","url":null,"abstract":"<div>\u0000 \u0000 <p>Five triphenylamine-based dyes were theoretically investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT) due to their structural configuration of (D–π–A) which has potential applications as sensitizers for dye-sensitized solar cells (DSSCs). One dye was sourced from the literature, (E)-2-cyano-3-(5-(6-(diphenylamino)-3,3-dimethyl-3H-indol-2-yl)thiophen-2-yl)acrylic acid, denoted as (I), and the remaining dyes (from II to V) are inspired by the former with minor structural change in the indole moiety of donor part. These molecular structures are composed of different diphenyl indole amine species (donor part), thiophene (π-bridge), and cyanoacrylic acid (acceptor part). This study focused on the effect of small structural change in the five-membered ring of the indole moiety on the geometric, electronic, and optical properties of the studied dyes as well as their potential applications as sensitizers for DSSCs. Due to this structural change, a twist in the molecular skeleton of the designed dyes was observed, resulting in a new band at a longer wavelength that spans the visible region. This band is attributed to the phenomenon of twisting intramolecular charge transfer (TICT). The findings reveal that the minor structural change in the indole moiety enhanced the harvesting character of designed dyes that makes them promising candidates for application in DSSCs.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 4","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431244","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}

引用次数: 0

Unexpected Inhibition of the Knoevenagel Condensation in Methanol by Iodonium Salt Served as Electrophilic Activator

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-14 DOI: 10.1002/poc.70006

Alexandra A. Sysoeva

引用次数: 0

False Identification of (Anti)aromaticity in Polycyclic Molecules in Ground and Excited States Through Incorrect Use of NICS

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-10 DOI: 10.1002/poc.70000

Péter J. Mayer, Henrik Ottosson

{"title":"False Identification of (Anti)aromaticity in Polycyclic Molecules in Ground and Excited States Through Incorrect Use of NICS","authors":"Péter J. Mayer, Henrik Ottosson","doi":"10.1002/poc.70000","DOIUrl":"https://doi.org/10.1002/poc.70000","url":null,"abstract":"<p>Aromaticity is a key concept in physical organic chemistry. However, as it cannot be measured directly, it is assessed indirectly via other properties (energetic, electronic, geometric and magnetic). Although these properties describe aromaticity, they are not solely related to aromaticity as the observed values also can stem from, for example, magnetically induced local currents at certain atoms or groups, or strain in the σ-skeleton. This can lead to misinterpretations. Here, we highlight a pitfall in the (anti)aromaticity assessment of polycyclic molecules when it is mainly based on nucleus independent chemical shifts (NICSs). The NICS index can be misinterpreted to indicate ‘aromaticity’ or ‘antiaromaticity’ in nonaromatic rings as a result of paratropic or diatropic ring currents in adjacent rings. We explore if such false indications by NICS are (i) stronger in Baird-aromatic or -antiaromatic excited states (mainly triplet and quintet, but also singlet) than in closed-shell singlet ground states, and (ii) if a paratropic ring current in an adjacent ring causes stronger or weaker false ‘aromaticity’ than a diatropic one causes false ‘antiaromaticity’. Based on our computations we conclude that larger aromatic rings in all types of states (e.g., a triplet state Baird-aromatic cyclooctatetraene ring) have greater influence than smaller ones, yet, we see no indication that the effect is stronger in excited states. Instead, annulene rings are more influential in their paratropic (antiaromatic) states, regardless if ground or excited states, than in their diatropic (aromatic) ones.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 3","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.70000","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143380823","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}

引用次数: 0

Periselectivity, Chemoselectivity, and Regioselectivity of the Cycloaddition Reaction of Aza-Oxyallyl Cations With Cinnamaldehyde: A Density Functional Theory Study

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-02-10 DOI: 10.1002/poc.70003

Godfred Boakye Adusei, Albert Aniagyei, Elliot Menkah, Caroline R. Kwawu, Gabriel Amankwah, Richmond Arhin, Hawa Osman, Evans Adei

引用次数: 0

DFT Insights Into Non-Catalytic Aminolysis of Polycarbonates

IF 1.9 4区化学

Journal of Physical Organic Chemistry Pub Date : 2025-01-28 DOI: 10.1002/poc.70001

Alexander Y. Samuilov, Amran Abdullah Ghilan Ali, Yakov D. Samuilov

{"title":"DFT Insights Into Non-Catalytic Aminolysis of Polycarbonates","authors":"Alexander Y. Samuilov, Amran Abdullah Ghilan Ali, Yakov D. Samuilov","doi":"10.1002/poc.70001","DOIUrl":"https://doi.org/10.1002/poc.70001","url":null,"abstract":"<div>\u0000 \u0000 <p>The problem of environmental pollution by plastic is becoming more and more obvious. In this study, the non-catalytic reaction of diphenyl carbonate with methylamine as a model reaction for the depolymerization of polycarbonate was studied at the B3LYP/6-31++G(d,p) and M062X/6-31++G(d,p) levels. The reaction can proceed by the nucleophilic substitution and by the “addition–elimination” pathways. Calculations at the B3LYP/6-31++G(d,p) level indicate that the reaction of diphenyl carbonate with methylamine monomer leading to the formation of N-methyl-O-phenylcarbamate via the nucleophilic substitution pathway at 298 K is characterized by activation and reaction free energies equal to 174.0 and −57.1 kJ·mol<sup>−1</sup>. The same reaction with methylamine dimer is characterized by activation and reaction free energies equal to 147.1 and −77.7 kJ·mol<sup>−1</sup>, respectively. Thermodynamic and kinetic preference is also observed in the reaction of N-methyl-O-phenylcarbamate with the monomer and dimer of methylamine. Reactions with the formation of tetrahedral intermediates are unlikely. Their formation is endothermic and occurs with a decrease in entropy. This leads to small values of equilibrium constants. The equilibrium constant of the reaction of diphenyl carbonate with methylamine monomer to form a tetrahedral intermediate is 1.64·10<sup>−16</sup> at 298 K and 1.20·10<sup>−14</sup> at 423 K. The same trends are observed in the reactions of N-methyl-O-phenylcarbamate. The reactions of diphenyl carbonate, N-methyl-O-phenylcarbamate with methylamine dimer via the “addition–elimination” pathway are also characterized by small values of equilibrium constants. In all cases, interactions involving the methylamine dimer are more favorable than reactions involving the methylamine monomer.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 3","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143120056","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}

引用次数: 0