Regioselectivity in Electrophilic Aromatic Substitution: Insights from Interaction Energy Decomposition Potentials

Fievez, Tim; Pintér, Balázs; Geerlings, Pau̧l; Bickelhaupt, F. Matthias; Proft, Frank De

doi:10.1002/ejoc.201001318

Cited by 20 publications

(18 citation statements)

References 49 publications

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“…To determine the intrinsic reactivity of linear acenes and the dependency of the reaction on the length of the acene, the interaction of the acene with an incoming electrophile was probed as outlined above. We established in our earlier study, concerning the orientation rules of S E Ar reactions,24 that the spherical and closed shell copper(I) is an ideal model soft electrophilic reagent that is capable of reliably characterizing the electrophilic reactivity of substituted aromatic systems. Moreover, we tested the consistency and regioselectivity‐predicting ability of our protocol in the latter study and established an ideal substrate–reagent distance, which can be used with confidence in the scanning procedure.…”

Section: Resultsmentioning

confidence: 99%

“…Our methodology for evaluating the intrinsic reactivity of linear acenes is straightforward and was presented previously24 for the case of substituted benzene derivatives: for electrophilic reactivity, as illustrated in Figure 1, a model soft electrophile,24,25 is moved along a rectangular grid parallel to the plane of the acene, and the interaction energy between the aromatic system and the electrophile is determined in every point of the grid. The origin of the grid, [0,0], was set to the center of mass of the acene, and axes x and y were chosen to be perpendicular and parallel with the C1–C2 bond, respectively (see Scheme for numbering in anthracene).…”

Section: Methodology and Computational Detailsmentioning

confidence: 99%

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Revealing the Origins of Electrophilic Reactivity and Regioselectivity of Linear Acenes Using Interaction Energy Decomposition Potentials

et al. 2013

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The intrinsic electrophilic reactivity of linear acenes up to octacene was investigated by using interaction energy potentials and their components, namely Pauli repulsion, orbital interaction, and electrostatic interaction potentials using the Ziegler–Rauk decomposition scheme. We found that the shared regions above C1 and C2 of the outer ring are slightly more attractive towards an incoming electrophile than the inner ring secondary carbon atoms, mostly due to a more advantageous electrostatic interaction. This result agrees with the stability order of prereactive π complexes formed between anthracene and the electrophilic HCl. Decomposition potentials determined in the bond formation regime indicate that longer acenes become more reactive because of the increasing orbital interaction. In addition, the orbital interaction potentials, which represent the overall effect of the high lying reactive orbital, exhibit straightforward patterns, predicting strongly preferred inner ring secondary carbon atoms over outer ring carbon atoms. Such an orbital‐interaction controlled regioselectivity shows up in the total interaction energy potentials when the electrostatic interaction is scaled down, predicting the functionalization of acenes with electrophiles on the inner secondary carbon atoms, in agreement with the experimental regioselectivity. Upon analyzing the stability of transition states for the addition of HCl to anthracene, the Pauli repulsion shows up to be an important factor in controlling the stability of the transition states and favoring functionalization along the central C9 and C10 positions to outer ring carbon atoms. The resonance stabilization concept, which is generally accepted to account for the regioselectivity of higher acenes, could not be evidenced by our analysis.

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Section: Resultsmentioning

confidence: 99%

Section: Methodology and Computational Detailsmentioning

confidence: 99%

Revealing the Origins of Electrophilic Reactivity and Regioselectivity of Linear Acenes Using Interaction Energy Decomposition Potentials

et al. 2013

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“…Although π complex formation shifts the electron densities at the different ring positions, V C of the initial reactants may, nevertheless, be related to reactivity. In this regard, a recent83 theoretical interaction energy decomposition analysis of the S E Ar reaction found that intrinsic properties of both the aromatic reactant and the electrophile can be used as reactivity and regioselectivity indicators.…”

Section: The Electrophile Affinity Indexmentioning

confidence: 99%

Structure–reactivity relationships for aromatic molecules: electrostatic potentials at nuclei and electrophile affinity indices

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Ilieva

Koleva

et al. 2012

WIREs Comput Mol Sci

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Recent advances have been achieved in the quantitative description of the reactivity of aromatic compounds in terms of simple parameters derived from theoretical computations. The first part of this review surveys the use of electrostatic potentials at nuclei (EPN) in characterizing the reactivity of substituted aromatic compounds when the reaction center is situated outside the aromatic ring. The application of EPN for several typical reactions of substituted aromatic systems is described in detail. The performance of alternative reactivity descriptors, such as theoretical atomic charges, the Parr electrophilicity index, and the experimental Hammett constants, is considered as well. The second part of this review discusses the recently proposed electrophile affinity construct for quantifying reactivity and regiospecificity for the most typical reaction of arenes: electrophilic aromatic substitution. The characterization of reactivity of aromatic molecules in terms of proton affinities and arene nucleophilicity indices is surveyed briefly. C 2012 John Wiley & Sons, Ltd.

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“…As every fresh organic chemistry student learns, both inductive as well as resonance or mesomeric components are usually invoked to rationalize the experimentally observed behavior. Rules to predict the ortho -/ para - or meta -orienting ability of substituents are an active topic in chemical research and have been recovered from almost every imaginable point of view [ 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 ]; and even the EAS reaction mechanism is still under debate [ 30 , 42 , 43 , 44 , 45 , 46 , 47 ]. Among the various previous approaches for EAS study, we are especially interested in the ELF due to its direct relation with the BCM model and the IQA-ELF coupling.…”

Section: Introductionmentioning

confidence: 99%

Energetics of Electron Pairs in Electrophilic Aromatic Substitutions

et al. 2021

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The interacting quantum atoms approach (IQA) as applied to the electron-pair exhaustive partition of real space induced by the electron localization function (ELF) is used to examine candidate energetic descriptors to rationalize substituent effects in simple electrophilic aromatic substitutions. It is first shown that inductive and mesomeric effects can be recognized from the decay mode of the aromatic valence bond basin populations with the distance to the substituent, and that the fluctuation of the population of adjacent bonds holds also regioselectivity information. With this, the kinetic energy of the electrons in these aromatic basins, as well as their mutual exchange-correlation energies are proposed as suitable energetic indices containing relevant information about substituent effects. We suggest that these descriptors could be used to build future reactive force fields.

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Regioselectivity in Electrophilic Aromatic Substitution: Insights from Interaction Energy Decomposition Potentials

Cited by 20 publications

References 49 publications

Revealing the Origins of Electrophilic Reactivity and Regioselectivity of Linear Acenes Using Interaction Energy Decomposition Potentials

Revealing the Origins of Electrophilic Reactivity and Regioselectivity of Linear Acenes Using Interaction Energy Decomposition Potentials

Structure–reactivity relationships for aromatic molecules: electrostatic potentials at nuclei and electrophile affinity indices

Energetics of Electron Pairs in Electrophilic Aromatic Substitutions

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