Journal of Physical Organic Chemistry最新文献

{"title":"Unexpected Inhibition of the Knoevenagel Condensation in Methanol by Iodonium Salt Served as Electrophilic Activator","authors":"Alexandra A. Sysoeva","doi":"10.1002/poc.70006","DOIUrl":"https://doi.org/10.1002/poc.70006","url":null,"abstract":"<div>\u0000 \u0000 <p>Halogen bond donors are recognized as electrophilic catalysts in reactions involving carbonyl compounds. This study describes an unexpected inhibition of the Knoevenagel condensation by the catalyst. To elucidate the intricacies of the inhibition mechanism, the overall reaction order and rate constants were determined using ¹H NMR spectroscopy, and further experiments with different nucleophiles were conducted. The findings revealed that the inhibition of the primary reaction is attributed to a substantial acceleration of the side reaction involving aldehyde methanolysis, which hinders the formation of the final alkene product.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 3","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143423967","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":"False Identification of (Anti)aromaticity in Polycyclic Molecules in Ground and Excited States Through Incorrect Use of NICS","authors":"Péter J. Mayer,&nbsp;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}

{"title":"Periselectivity, Chemoselectivity, and Regioselectivity of the Cycloaddition Reaction of Aza-Oxyallyl Cations With Cinnamaldehyde: A Density Functional Theory Study","authors":"Godfred Boakye Adusei,&nbsp;Albert Aniagyei,&nbsp;Elliot Menkah,&nbsp;Caroline R. Kwawu,&nbsp;Gabriel Amankwah,&nbsp;Richmond Arhin,&nbsp;Hawa Osman,&nbsp;Evans Adei","doi":"10.1002/poc.70003","DOIUrl":"https://doi.org/10.1002/poc.70003","url":null,"abstract":"<div>\u0000 \u0000 <p>This study theoretically investigates the factors controlling the periselectivity, chemoselectivity, and regioselectivity of the [3 + 2] cycloaddition reaction of aza-oxyallyl cation with cinnamaldehyde to form oxazolidinone. The research utilizes hybrid density functional theory (DFT) method at the B3LYP-D3, B3LYP, M06, and M062X coupled with the 6-311G (d, p) level of theories to explain that the [3 + 2] chemoselective addition of aza-oxyallyl cation across the carbonyl bond of cinnamaldehyde through its C and N reactive sites is more favorable than any other plausible mechanism. Generally, electron-donating groups (EDGs) on aza-oxyallyl cation decrease the activation barriers, whereas electron-withdrawing groups (EWGs) increase the activation barrier. The GEDT values predict a very low polar reaction for the [3 + 2] cycloaddition reaction.</p>\u0000 </div>","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":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143380822","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":"DFT Insights Into Non-Catalytic Aminolysis of Polycarbonates","authors":"Alexander Y. Samuilov,&nbsp;Amran Abdullah Ghilan Ali,&nbsp;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⁻¹. The same reaction with methylamine dimer is characterized by activation and reaction free energies equal to 147.1 and −77.7 kJ·mol⁻¹, 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 1.64·10⁻¹⁶ at 298 K and 1.20·10⁻¹⁴ 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}

{"title":"Rigidity Analysis of Hydride Tunneling-Ready States From Secondary Kinetic Isotope Effects and Hammett Correlations: Relating to the Temperature Dependence of Kinetic Isotope Effects","authors":"Mingxuan Bai,&nbsp;Grishma Singh,&nbsp;Yun Lu","doi":"10.1002/poc.70002","DOIUrl":"https://doi.org/10.1002/poc.70002","url":null,"abstract":"<div>\u0000 \u0000 <p>Recent study on the effects of enzyme mutations on the primary kinetic isotope effects (1° KIEs) of H-tunneling reactions revealed that a more rigid system results in a weaker temperature dependence of KIEs, indicated by a smaller isotopic activation energy difference (∆<i>E</i>_a = <i>E</i>_aD − <i>E</i>_aH). In literature, a more rigid system has been defined by the presence of shorter, more densely populated hydrogen donor-acceptor distances (DADs) in both the productive reactant complexes (PRCs) and the tunneling-ready states (TRSs). Studying the relationship between DAD_PRC/DAD_TRS and ∆<i>E</i>_a can help validate existing H-tunneling models or guide the development of new theories. In a previous publication, we employed Hammett correlations on hydride acceptors (NAD⁺ analogues) to propose TRS electronic structures for qualitative analysis of DAD_TRS order. In this paper, we selected a pair of such systems and used secondary (2°) KIEs on the hydride donor (NADH analogue) to obtain quantitative DAD_TRS information at the molecular level. TRS structures were computed, and the corresponding 2° KIEs were calculated and fitted to the observed values to extract DAD_TRS data. PRC structures were also computed. The DAD_PRC/DAD_TRS information aligns with the rigidity order derived from Hammett correlation analysis, and the correlation between DAD_PRC/DAD_TRS and ∆<i>E</i>_a is consistent with observations in enzyme systems.</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":"143120013","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":"Machine Learning Enabling the Prediction of Activation Energies of SPAAC","authors":"Jason D. Josephson,&nbsp;John Paul Pezacki,&nbsp;Masaya Nakajima","doi":"10.1002/poc.4679","DOIUrl":"https://doi.org/10.1002/poc.4679","url":null,"abstract":"<div>\u0000 \u0000 <p>This study leverages machine learning to predict the activation energies of strain-promoted azide-alkyne cycloaddition (SPAAC) reactions. Using DFT calculations, 631 sets of bond angles and Mulliken charges from two acyclic alkynes were collected. Multiple machine learning models were trained on these data, achieving high accuracy (<i>R</i>² &gt; 0.95). Both bond angle and charge were crucial for reliable predictions. The models successfully predicted activation energies for SPAAC reactions with unseen cycloalkynes, within certain limitations.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 2","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143115962","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 ESIPT for NHBQ-NO2 and NHBQ-NH2: A DFT/TDDFT Study","authors":"Wen Zeng,&nbsp;Wenlong Shao,&nbsp;Jinfeng Zhao,&nbsp;Jiahe Chen","doi":"10.1002/poc.4680","DOIUrl":"https://doi.org/10.1002/poc.4680","url":null,"abstract":"<div>\u0000 \u0000 <p>Inspired by distinguished characteristics of novel optical materials, there has been significant research interest in organic molecules that present excited-state intramolecular proton transfer (ESIPT) properties. Given the vital effects of substituent effect on molecular designs, in this study, we focus on probing into excited state behaviors of NHBQ-NO₂ (i.e., submitted by strong electron-withdrawing group -NO₂) and NHBQ-NH₂ (i.e., submitted by strong electron-donating group -NH₂). Exploring hydrogen bonding effects via photoexcitation, we verify the impact of substituent effect (-NO₂ and -NH₂) on interactions involving photo-induced hydrogen bonding effects, redistribution of charges, and associated phenomena related to ESIPT reaction. By comparing and quantifying the barriers for reactions in relative excited state, our results indicate electron-donating substituent -NH₂ enhances the ESIPT reaction for NHBQ fluorophore.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 2","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143111475","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":"Mechanistic Multiscale Simulations and Charge Transport Properties of Amorphous and Crystalline α-NPD Molecular Conformations: Insights From Molecule to Material Level","authors":"Simplice Koudjina,&nbsp;Vipin Kumar,&nbsp;Anuj Tripathi,&nbsp;Guy Yacole Sylvain Atohoun,&nbsp;Joachim Djimon Gbenou,&nbsp;Prabhakar Chetti","doi":"10.1002/poc.4677","DOIUrl":"https://doi.org/10.1002/poc.4677","url":null,"abstract":"&lt;div&gt;\u0000 \u0000 &lt;p&gt;The optoelectronic and charge transfer integral properties of N,N′-di(1-naphthyl)-N,N′-diphenyl-4,4′-diamine (α-NPD) organic light-emitting diode (OLED) in amorphous and crystalline structures is studied based on the Marcus–Levitch–Jortner theory and quantum chemistry calculations. The charge transfer integral simulations have been investigated through hole-hopping regime from molecule-to-molecule in dimers molecules and are determined by &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mtext&gt;HOMO&lt;/mtext&gt;\u0000 &lt;mo&gt;→&lt;/mo&gt;\u0000 &lt;mtext&gt;LUMO&lt;/mtext&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ mathrm{HOMO}to mathrm{LUMO} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; frontier molecular orbitals (FMOs) for hole and electron transport. Quantum approaches with TD/DFT and DFT have been used to describe the most relevant electronic transitions of α-NPD, which present &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mi&gt;π&lt;/mi&gt;\u0000 &lt;mo&gt;→&lt;/mo&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;π&lt;/mi&gt;\u0000 &lt;mo&gt;*&lt;/mo&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ pi to {pi}^{ast } $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; character in harmony with the solvent states. Furthermore, the obtained results reveal that geometric deformations have been relied to naphthalene form and benzene rings in α-NPD structures, and the charge transfer integral in amorphous state shows &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msub&gt;\u0000 &lt;mi&gt;t&lt;/mi&gt;\u0000 &lt;mtext&gt;hole&lt;/mtext&gt;\u0000 &lt;/msub&gt;\u0000 &lt;mo&gt;=&lt;/mo&gt;\u0000 &lt;mn&gt;4.46&lt;/mn&gt;\u0000 &lt;mspace&gt;&lt;/mspace&gt;\u0000 &lt;mi&gt;meV&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {t}_{mathrm{hole}}=4.46 mathrm{meV} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; and &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msub&gt;\u0000 &lt;mi&gt;t&lt;/mi&gt;\u0000 &lt;mtext&gt;elec&lt;/mtext&gt;\u0000 &lt;/msub&gt;\u0000 &lt;mo&gt;=&lt;/mo&gt;\u0000 &lt;mn&gt;3.18&lt;/mn&gt;\u0000 &lt;mspace&gt;&lt;/mspace&gt;\u0000 &lt;mi&gt;meV&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {t}_{mathrm{elec}}=3.18 mathrm{meV} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;, and in the crystalline state, it shows &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msub&gt;\u0000 &lt;mi&gt;t&lt;/mi&gt;\u0000 &lt;mtext&gt;hole&lt;/mtext&gt;\u0000 &lt;/msub&gt;\u0000 &lt;mo&gt;=&lt;/mo&gt;\u0000 &lt;mn&gt;4.25&lt;/mn&gt;\u0000 &lt;mspace&gt;&lt;/mspace&gt;\u0000 &lt;mi&gt;meV&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {t}_{mathrm{hole}}=4.25 mathrm{meV} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; and &lt;span&gt;&lt;/sp","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 2","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143110773","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":"Solvent-Assisted Prototopic Switching of Norharmane Along Hydrogen-Bonded Network: Assessing the Precise Length of Network","authors":"Suvendu Paul,&nbsp;Nilanjan Dey","doi":"10.1002/poc.4678","DOIUrl":"https://doi.org/10.1002/poc.4678","url":null,"abstract":"<div>\u0000 \u0000 <p>In this article, the proton transfer dynamics along a stable norharmane•(H₂O)_n (<i>n</i> = 2–4) hydrogen-bonded cluster on conversion from the neutral to cationic form of norharmane (<b>NHM</b>) in water medium was demonstrated experimentally and theoretically. The distinct absorption and emission bands of different prototropic forms of <b>NHM</b> are well-known in the literature. Initially, the conversion from neutral to cationic form of <b>NHM</b> on moving from a polar aprotic (acetonitrile) to a polar protic (water) solvent was ensured by steady-state absorption and fluorescence studies. The analysis of IR spectra and steady-state anisotropy data of <b>NHM</b> confirmed the possibility of the formation of a hydrogen-bonded network in the presence of water. The length of the network was explored and assumed by extensive Density Functional Theory (DFT) calculations. Then, by time-dependent density functional theory (TD-DFT), the excited state proton transfer (ESPT) pathway was established interrogating the <b>NHM</b>-water cluster with different numbers of water molecules. The theoretical analysis assured that the <b>NHM</b>•(H₂O)₂ cluster was incapable of maintaining the stable hydrogen bonding wire in the course of the ESPT mechanism. Rather, <b>NHM</b>•(H₂O)₃ and <b>NHM</b>•(H₂O)₄ clusters were simultaneously involved in operating the ESPT mechanism. The <b>NHM</b>•(H₂O)₄ cluster was more feasible to carry out the proton transfer than the <b>NHM</b>•(H₂O)₃ cluster. To the best of our knowledge, this was possibly the first theoretical evidence behind the conversion from neutral to cationic form of <b>NHM</b> via the formation of a hydrogen-bonded network.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 2","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143119148","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":"Bioorthogonal Reactions of Oxadiazinones With Strained trans-Cyclooctenes","authors":"Kaitlyn Morrill,&nbsp;Jason D. Josephson,&nbsp;Didier A. Bilodeau,&nbsp;Baha Altamimi,&nbsp;Masaya Nakajima,&nbsp;John Paul Pezacki","doi":"10.1002/poc.4674","DOIUrl":"https://doi.org/10.1002/poc.4674","url":null,"abstract":"<div>\u0000 \u0000 <p>We report quantitative details of addition reactions of a strained <i>trans</i>-cyclooctene with a series of oxadiazinones, analogues of the bioorthogonally fruitful tetrazines. Both experimental and computational studies of these ligations reveal their sensitivity to differing electronic character of oxadiazinone substituents. Achieving rate constants up to 9.5 L mol⁻¹ s⁻¹, oxadiazinones demonstrate untapped potential for bioorthogonal applications.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"38 2","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.4674","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143117879","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}