Aromaticity and chemical reactivity in isoindole

Chacko, Elsamma; Börnstein, J.; Sardella, D. J.

doi:10.1016/s0040-4039(01)92840-0

Cited by 14 publications

(6 citation statements)

References 15 publications

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“…[3][4] Previous studies concerning the aromaticity of 2 indicate that this compound is considerably less aromatic than 1 with a difference in resonance energies of 12.2 kcal.mol -1 . 5 Additionally, Sardella and coworkers 6 suggest that 2 can be best understood in terms of the interaction between pyrrole ring and 1,3-cis-butadiene in C3 and C4 carbons (see 5MR ring numeration in Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

“…3,4 Previous studies concerning the aromaticity of 2 indicate that this compound is considerably less aromatic than 1 with a difference in resonance energies of 12.2 kcal•mol −1 . 5 Additionally, Sardella and co-workers 6 suggest that 2 can be best understood in terms of the interaction between the pyrrole ring and 1,3-cis-butadiene in C3 and C4 carbons (see 5MR ring numeration in Figure 1). These results coincide with the work by Mandado et al, 7 who systematically evaluated the aromaticity of azines, noting that the aromaticity of the 6MR in 1 is greater than that of 2 and finding the opposite case for the 5MR.…”

Section: ■ Introductionmentioning

confidence: 99%

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The Relative Stability of Indole Isomers Is a Consequence of the Glidewell-Lloyd Rule

Pino‐Rios

Solà

2020

J. Phys. Chem. A

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Indole (1) is a heterocyclic aromatic compound consisting of a pyrrole ring (5MR) fused with a benzene ring (6MR). This compound is highly stable, found in several natural products, and used as a building block for the synthesis of novel organic compounds. On the other hand, its isomers isoindole (2) and indolizine (3) are much less stable and are normally isolated when bonded to other stable compounds. The stability of these compounds has been analyzed in terms of local aromaticity using magnetic, geometric, and delocalization criteria. All criteria used indicate that there is a continuing reduction in aromaticity of the 6MR whereas, for the 5MR, the aromaticity increases when going from 1 to 3. This is confirmed by Natural Resonance theory calculations indicating that the resonant structures which retain the aromaticity of 5MR are the ones having the largest contribution.The results obtained suggest that the relative stability of indole isomers is a consequence of the Glidewell-Lloyd rule.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

The Relative Stability of Indole Isomers Is a Consequence of the Glidewell-Lloyd Rule

Pino‐Rios

Solà

2020

J. Phys. Chem. A

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“…26 Quantum chemical calculations yield principal components of the EFG tensor, q ii , in atomic units (1 au ¼ 9:717365 Â 10 2 1 Vm À2 ), 8 with jq zz j ! jq yy j !…”

Section: Methodsmentioning

confidence: 99%

“…Synthesis and characterization of various alkaloids containing isoindole have been reported 1 and used in plastics, chemical synthesis, researches. 2,3 The electronic structure of isoindole has been the subject of several studies, in which methods of quantum chemistry were used to exploring the di®erences in the ground state, [4][5][6][7] peculiarities of the reactivity, 8,9 and photophysical properties. 10,11 In solution, the isoindole tautomer is the predominant form and therefore the compound resembles a pyrrole more than a simple imine.…”

Section: Introductionmentioning

confidence: 99%

Tautomeric transformations and reactivity of isoindole and sila-indole: A computational study

Ghiasi

Fashami

2014

J. Theor. Comput. Chem.

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In this work, the tautomeric transformations and reactivity of isoindole and sila-isoindole molecules has been explored using the B3LYP/6-311G(d,p) level of theory in gas and solution phases. These calculations show that isoindole isomer has more stability rather than 1-h-isoindole. There is identical trend in silated species. The frontier molecular orbitals (FMO) and band gap energy calculations were performed at the B3LYP/6-311G(d,p) level in gas and various solvent. Solvent e®ects have been analyzed by using the self-consistent reaction¯eld (SCRF) method based on polarizable continuum model (PCM) in chloroform, chlorobenzene, dichloromethane and tetrahydrofurane. Thermodynamic parameters calculated at room temperature have been analyzed. Also, electron a±nities were computed. Local reactivity descriptors as Fukui functions (f þ k ; f À k f 0 k ) local softness (s þ k ; s À k s 0 k ) and electrophilicity indices (! þ k ; ! À k ; ! 0 k ) analyses are performed to¯nd out the reactive sites within molecule. Density functional theory (DFT) calculations were performed to compute nitrogen-14 nuclear quadrupole resonance (NQR) spectroscopy parameters.

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“…In fact, crystal structure determination of many IAA derivatives and some ab initio calculations on IAA 2 revealed systematically shortening of the bonds C4C5 and C6C7. Several papers 4, 5, 9–13 on aromaticity of indole and its isomers clearly showed that indole is a highly aromatic system, with the nitrogen free electron pair participating in electron delocalization as a requirement for indole's aromaticity 4 (the lone pair is formally equivalent to a double bond 11). The position of nitrogen in the pyrrole ring makes the indole more aromatic than its isomers 9, 13.…”

Section: Introductionmentioning

confidence: 99%

Combined computational and chemometric study of 1H‐indole‐3‐acetic acid

Kiralj

Ferreira

2003

Int J of Quantum Chemistry

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ABSTRACT:Geometries of free 1H-indole-3-acetic acid (IAA) and IAA hydrogen bond dimer were optimized at several computational levels: molecular mechanics, semiempirical methods, ab initio density functional theory with SVWN (Slater-VoskoWilk-Nusair) and Becke's three-parameter exchange functional and the gradientcorrected functional of Lee, Yang, and Paar (B3LYP) functionals, and Hartree-Fock (HF). Bond length matrices X(mxn) (m ϭ number of bonds, n ϭ number of experimental determinations and theoretical calculations) and their transposes X(nxm) for IAA monomer, IAA dimer, and hydrogen bond ring (angles included) were analyzed using principal component analysis (PCA) and hierarchical cluster analysis (HCA). Ab initio methods prove to be superior to molecular mechanics and semiempirical methods: SVWN methods are the best for monomer, and B3LYP are best for dimer geometry optimization. The B3LYP and HF methods can be used equally well for optimization of the dimer ring geometry. Other hydrogen bond and aromaticity structural parameters exhibit preference either for B3LYP or SVWN methods.

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Aromaticity and chemical reactivity in isoindole

Cited by 14 publications

References 15 publications

The Relative Stability of Indole Isomers Is a Consequence of the Glidewell-Lloyd Rule

The Relative Stability of Indole Isomers Is a Consequence of the Glidewell-Lloyd Rule

Tautomeric transformations and reactivity of isoindole and sila-indole: A computational study

Combined computational and chemometric study of 1H‐indole‐3‐acetic acid

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