DFT study of double 1,3-dipolar cycloaddition of nitrilimines with allenoates

Soleymani, Mousa

doi:10.1007/s00706-018-2311-y

Cited by 16 publications

(5 citation statements)

References 34 publications

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“…Today, numerous examples by different scientists all around the world, show that the concern of emergence of stereo impurities via the stepwise pathways for the 32CA processes is real [81][82][83][84][85][86][87][88][89][90][91][92][93][94][95][96][97][98][99][100]. Moreover, the accuracy of theoretical studies on the mechanism and kinetics of 32CA process have been confirmed by comparative quantum chemical investigations [101][102][103][104][105][106][107][108][109][110][111][112][113][114][115].…”

Section: Scheme 3 the Stepwise Mechanism Through The Zwitterionic Int...mentioning

confidence: 99%

The extraordinary gravity of three atom 4π-components and 1,3-dienes to C20-nXn fullerenes; a new gate to the future of Nano technology

Siadati

Rezazadeh

2022

Sci. Rad

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A quick glance to the adsorption, sensing, and energy storage abilities of C20 fullerene and its derivatives indicate that this small carbon cluster may have extraordinary properties which would make it a key part of the future of Nano actuators and Nano machines. For example, in the case of the gravity of three atom 4π-components (TACs) to these carbon cages, it should be noted that; the rate constants (K)s of the reaction of C20 fullerene with 1,3-butadiene (Diels-Alder (DA) process), and with 2-furan nitrile oxide ([3+2] cycloaddition (32CA process)) are 2.51(1011) M-1 s-1, and 1.4(107)M-1 s-1, respectively. However, the rate constant of the 32CAreaction between norbornadiene and 3,4-dihydro isoquinoline-N-oxide is about 2.56(10-5) M-1 s-1 (both by DFT and by experimental results). This simple comparison could show the extraordinary gravity of some TACs and dienes to C20 fullerenes.

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Section: Scheme 3 the Stepwise Mechanism Through The Zwitterionic Int...mentioning

confidence: 99%

The extraordinary gravity of three atom 4π-components and 1,3-dienes to C20-nXn fullerenes; a new gate to the future of Nano technology

Siadati

Rezazadeh

2022

Sci. Rad

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“…To make calculations more realistic, solvation effects (using dichloromethane as solvent) have been taken into account using the conductor-like polarizable continuum model (CPCM) [ 36 , 37 ]. Dichloromethane was chosen as a model solvent for a correct comparison with the available literature data, since most of the literature data for DFT modeling of reactions involving nitrile imines are given for dichloromethane [ 38 , 39 ]. In the calculations of the condensed Fukui functions [ 40 ], the cationic and anionic systems were kept at the optimized geometries of the corresponding neutral systems.…”

Section: Resultsmentioning

confidence: 99%

Regioselective Cycloaddition of Nitrile Imines to 5-Methylidene-3-phenyl-hydantoin: Synthesis and DFT Calculations

Filkina

Baray

Белоглазкина

et al. 2023

IJMS

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Nitrile imine cycloaddition to hydantoins containing an exocyclic C=C double bond has been previously described in a very limited number of examples. In this work, regioselective synthesis of spiro-pyrazoline-imidazolidine-2,4-diones based on a 1,3-dipolar cycloaddition reaction of nitrile imines to 5-methylidene-3-phenyl-hydantoin have been proposed. It was found that, regardless of the nature of the aryl substituents at the terminal C and N atoms of the C-N-N fragment of nitrile imine (electron donor or electron acceptor), cycloaddition to the 5-methylidenhydantoin exocyclic C=C bond proceeds regioselectively, and the terminal nitrogen atom of the nitrile imine connects to the more sterically hindered carbon atom of the double bond, which leads to the formation of a 5-disubstituted pyrazoline ring. The observed cycloaddition regioselectivity was rationalized using DFT calculations of frontier molecular orbital interactions, global CDFT reactivity indices, and minimum energy paths.

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“…Negative values of activation entropy indicate that all the transition states have less degree of freedom as compared to the corresponding reacting species [55].…”

Section: Resultsmentioning

confidence: 99%

“…These maps display the distribution of electron density on molecules; different colors depict different values of electron density. Red color indicates the high electron density while blue color shows electron de cient site[55, 62]. MESP has been utilized for understanding many important problems in chemistry e.g.…”

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confidence: 99%

Quantum Mechanical Modeling Unveil the Effect of Substitutions on the Activation Barriers of the Diels-Alder Reactions of an Antiviral Compound 7H-Benzo[a]phenalene

Rehman

Mansha

Zahid

et al. 2021

Preprint

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Density functional theory has been utilized for exploring the mechanism of Diels-Alder reaction between 7H-benzo[a]phenalene and maleic anhydride. 7H-Benzo[a]phenalene is an antiviral compound and information available about its cycloaddition reactions with possible reaction path and mechanism is scarce. In order to work on the synthesis of its further potential derivatives, the mechanism of its reaction with all aspects should be well understood. Two novel intermediates involved in this reaction have been reported. Diels-Alder reaction of maleic anhydride has found many applications in the synthesis of wide range of useful products. The major concern of this work is to evaluate the consequences of introducing electron donating and electron withdrawing substituents on the reactivity of maleic anhydride towards 7H-benzo[a]phenalene. Thermodynamic parameters, activation parameters, energies of frontier orbitals, global reactivity indices and global electron density transfer (GEDT) have been determined for all the reactions. Fukui functions are computed for each reactant in order to identify the most reactive sites. All the reactions have been found to proceed via normal electron demand having polar nature. The substituents with opposite electronic properties were expected to affect the reactivity of dienophile in an inverse manner, however, the results are not according to this assumption. Rather, both kinds of substituents increased the activation barrier of the reaction. This behavior has been explained in the light of various parameters such as the stability of reacting species, gap of frontier molecular orbitals etc. Experimental studies reported previously are in agreement with these results.

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DFT study of double 1,3-dipolar cycloaddition of nitrilimines with allenoates

Cited by 16 publications

References 34 publications

The extraordinary gravity of three atom 4π-components and 1,3-dienes to C20-nXn fullerenes; a new gate to the future of Nano technology

The extraordinary gravity of three atom 4π-components and 1,3-dienes to C20-nXn fullerenes; a new gate to the future of Nano technology

Regioselective Cycloaddition of Nitrile Imines to 5-Methylidene-3-phenyl-hydantoin: Synthesis and DFT Calculations

Quantum Mechanical Modeling Unveil the Effect of Substitutions on the Activation Barriers of the Diels-Alder Reactions of an Antiviral Compound 7H-Benzo[a]phenalene

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