Multidimensional Isotropic Magnetic Shielding Contour Maps for the Visualization of Aromaticity in ortho-Arynes and Their Reactions

Artigas, Albert; Hagebaum‐Reignier, Denis; Carissan, Yannick; Coquerel, Yoann

doi:10.1055/a-1867-0674

Cited by 4 publications

(3 citation statements)

References 35 publications

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“…The ongoing interest in this topic is evidenced by the remarkable number of recent articles involving experimental and/or theoretical studies (selected examples are cited in this work). [1][2][3][4][5][6][7][8][9][10][11] A major contributing factor in the revival of interest in aromaticity is the application of polycyclic aromatic hydrocarbons (PAHs) or polyarenes in materials science, particularly in the area of organic electronics. [11,12] Modulation of their molecular properties, in particular the highest occupied molecular orbital (HOMO)lowest unoccupied molecular orbital (LUMO) energy gap (ΔE HÀ L ), is critical for the design of organic optoelectronic devices, [12][13][14][15][16] and conductive materials.…”

Section: Introductionmentioning

confidence: 99%

“…Aromaticity is a pivotal concept in organic chemistry that continues to be an active field of research for both fundamental and applied purposes. The ongoing interest in this topic is evidenced by the remarkable number of recent articles involving experimental and/or theoretical studies (selected examples are cited in this work) [1–11] . A major contributing factor in the revival of interest in aromaticity is the application of polycyclic aromatic hydrocarbons (PAHs) or polyarenes in materials science, particularly in the area of organic electronics [11,12] .…”

Section: Introductionmentioning

confidence: 99%

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Gauging the Aromatic, Antiaromatic, and Nonaromatic Character of the Dications and Dianions Derived from Fused Carbocyclic and Heterocyclic Compounds^ǂ

Borosky,

Laali

2023

ChemistrySelect

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Dications and dianions derived from fused PAHs and hetero‐PAHs were investigated by means of DFT calculations. The electronic, energetic, and structural features of the singlet and triplet electronic states of these doubly charged species were computationally determined and compared with those of the corresponding neutral parent aromatic and heteroaromatic compounds. The aromatic, nonaromatic or antiaromatic character of the studied diions was evaluated via magnetic criteria, namely NICS and 1H NMR chemical shifts, and by the HOMA structural index. Linear correlations were revealed between the computed HOMO‐LUMO gaps and the magnetic parameters which could serve as a guiding tool in the modulation of molecular properties, and for designing new materials derived from this type of compounds.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Gauging the Aromatic, Antiaromatic, and Nonaromatic Character of the Dications and Dianions Derived from Fused Carbocyclic and Heterocyclic Compounds^ǂ

Borosky,

Laali

2023

ChemistrySelect

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“…Arynes are electrophilic species that generally react with nucleophiles in addition reactions, and with unsaturated molecules in cycloaddition reactions. Theoretical analyses of the electronic structure and aromaticity of arynes using magnetic criteria showed that arynes are aromatic species and are better described as acetylene-containing rather than cumulene-containing molecules . But it should be kept in mind that the traditional Lewis structure of arynes with a triple bond is an oversimplification.…”

Section: Introductionmentioning

confidence: 99%

Determination of the Rate Constant of the [4 + 2] Cycloaddition Between an Aryne Atropisomer and Furan in Solution

et al. 2022

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Using a specially designed prototype of a nonracemic aryne atropisomer with a low barrier to enantiomerization (ca. 36 kJ·mol–1), it was possible to determine the kinetic constant of its cycloaddition with furan in solution by a combination of theoretical calculations and experimental measurements. It was found that the reaction half-life of this aryne atropisomer in solution with 100 equivalents of furan as the trapping reagent is <150 ns at temperatures above −20 °C.

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Aryne Atropisomers: Chiral Arynes for the Enantiospecific Synthesis of Atropisomers and Nanographene Atropisomers

Coquerel

2023

Acc. Chem. Res.

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Conspectus The basics about arynes and their applications in synthetic organic chemistry are briefly presented, and the concept of atropisomerism is defined, highlighting that it is a time-dependent form of isomerism and chirality. It is remembered that racemization is a macroscopic and statistical irreversible process, while enantiomerization is a nanoscopic reversible process that occurs at the molecular scale, with racemization being twice as fast as enantiomerization. The concept of aryne atropisomers is introduced with a naive question: Can synthetically useful nonracemic aryne atropisomers having a triple bond ortho to the stereogenic single bond exist in solution? It was found that such aryne atropisomers can be generated in solution from easily available ortho-iodoaryl triflate precursors and excess trimethylsilylmethylmagnesium chloride. Analysis of the barriers to enantiomerization of some aryne atropisomers by computational modeling revealed the key contribution to the configurational stability of the H atom in tris-ortho-substituted biphenyl-based atropisomers. Using a specially designed prototype of aryne atropisomer, for which the barrier to enantiomerization was accurately evaluated by advanced computational modeling, the kinetic parameters of its reaction with furan were experimentally determined. From these measurements, it was concluded that any aryne atropisomer with a barrier to enantiomerization ΔG enant ⧧ equal to or higher than 50 kJ mol–1 would lead to fully enantiospecific reactions. The synthetic applications of two structurally distinct aryne atropisomers built on a 1-phenylnaphthalene platform are described: one has the aryne triple bond embedded in the naphthyl moiety, and the other has the aryne triple bond embedded in the phenyl moiety. Both aryne atropisomers allowed for the fully enantiospecific, and possibly overall enantioselective, syntheses of original atropisomers based on standard aryne chemistry. For instance, reactions with anthracene and perylene afforded triptycene and nanographene atropisomers, respectively, in high enantiomeric excesses. A bis(aryne) atropisomer synthetic equivalent prepared from either enantiomer of BINOL is described for 3D bidirectional reactions with a single handedness. Its 2-fold reactions with anthracene and perylene afforded the corresponding severely congested bis(benzotriptycene) (99% ee) nanocarbon atropisomer and bis(anthra[1,2,3,4-ghi]perylene) (98% ee) nanographene atropisomer, respectively. This allowed the discovery of bis(twistacene) atropisomers as a new class of polycyclic aromatic hydrocarbons (PAH) with multiple stereogenicities. Cross reactions with the bis(aryne) atropisomer synthetic equivalent and two different arynophiles proved feasible, providing a nanographene atropisomer with a benzotriptycene unit and an anthra[1,2,3,4-ghi]perylene unit assembled around a stereogenic axis as a unique chiral PAH (99% ee). Overall, because the concept is simple and its implementation is easy, aryne atropisomers is an attractive approach to ...

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Multidimensional Isotropic Magnetic Shielding Contour Maps for the Visualization of Aromaticity in ortho-Arynes and Their Reactions

Cited by 4 publications

References 35 publications

Gauging the Aromatic, Antiaromatic, and Nonaromatic Character of the Dications and Dianions Derived from Fused Carbocyclic and Heterocyclic Compounds^ǂ

Gauging the Aromatic, Antiaromatic, and Nonaromatic Character of the Dications and Dianions Derived from Fused Carbocyclic and Heterocyclic Compounds^ǂ

Determination of the Rate Constant of the [4 + 2] Cycloaddition Between an Aryne Atropisomer and Furan in Solution

Aryne Atropisomers: Chiral Arynes for the Enantiospecific Synthesis of Atropisomers and Nanographene Atropisomers

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Multidimensional Isotropic Magnetic Shielding Contour Maps for the Visualization of Aromaticity in ortho-Arynes and Their Reactions

Cited by 4 publications

References 35 publications

Gauging the Aromatic, Antiaromatic, and Nonaromatic Character of the Dications and Dianions Derived from Fused Carbocyclic and Heterocyclic Compoundsǂ

Gauging the Aromatic, Antiaromatic, and Nonaromatic Character of the Dications and Dianions Derived from Fused Carbocyclic and Heterocyclic Compoundsǂ

Determination of the Rate Constant of the [4 + 2] Cycloaddition Between an Aryne Atropisomer and Furan in Solution

Aryne Atropisomers: Chiral Arynes for the Enantiospecific Synthesis of Atropisomers and Nanographene Atropisomers

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Product

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Gauging the Aromatic, Antiaromatic, and Nonaromatic Character of the Dications and Dianions Derived from Fused Carbocyclic and Heterocyclic Compounds^ǂ

Gauging the Aromatic, Antiaromatic, and Nonaromatic Character of the Dications and Dianions Derived from Fused Carbocyclic and Heterocyclic Compounds^ǂ