Site-, enantio- and stereo-selectivities of the 1,3-dipolar cycloaddition reactions of oxanorbornadiene with C,N-disubstituted nitrones and dimethyl nitrilimines: a DFT mechanistic study

Opoku, Ernest; Arhin, Grace; Pipim, George Baffour; Adams, Anita Houston; Tia, Richard; Adei, Evans

doi:10.1007/s00214-019-2529-8

Cited by 26 publications

(8 citation statements)

References 29 publications

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“…The analysis of obtained results show that LUMO energies of the investigated molecules are higher than ITO, which equals (-4.7 ev). This indicates that the excited state molecules have a considerable capacity to inject electrons into the ITO electrodes [19].…”

Section: Organic Compounds Optimizationmentioning

confidence: 99%

DFT and TD-DFT calculation of new aryl cyanomethylene-quinone mono-oximes-based small molecules for organic photovoltaic

Lakrikh

Hachim

Ghaleb

2023

Preprint

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We calculated electrical characteristics of eight compounds based on aryl-cyano-methylene-quinone mono-oximes using density functional theory (DFT) with base set B3LYP/6-311G (d). Some of theoretical factors, such as energy of HOMO (EHOMO), energy of LUMO (ELUMO), and Gap energy (Egap) are highly relevant in the photovoltaic sector. On the other hand, we investigated our results by determining electronic and spectroscopic properties using TD-DFT and with base set B3LYP/6-311G (d), in order to define the wavelengths of studied molecules, tracing the visible and ultra-violet spectrum, and determine the transition states. The achieved results and developed attributes show that these molecules could be extremely efficient in the renewable energy industry.

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Section: Organic Compounds Optimizationmentioning

confidence: 99%

DFT and TD-DFT calculation of new aryl cyanomethylene-quinone mono-oximes-based small molecules for organic photovoltaic

Lakrikh

Hachim

Ghaleb

2023

Preprint

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“…Very recently, two different studies [20,21] have addressed the regio-, stereo-, and enantioselectivities of the 32CA reactions of 7-isopropylidenenorbornadiene and oxonorbornadiene with nitrones, azides, and nitrileimines.…”

Section: Introductionmentioning

confidence: 99%

Unveiling the Unexpected Reactivity of Electrophilic Diazoalkanes in [3+2] Cycloaddition Reactions within Molecular Electron Density Theory

2021

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The [3+2] cycloaddition (32CA) reactions of strongly nucleophilic norbornadiene (NBD), with simplest diazoalkane (DAA) and three DAAs of increased electrophilicity, have been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G (d,p) computational level. These pmr-type 32CA reactions follow an asynchronous one-step mechanism with activation enthalpies ranging from 17.7 to 27.9 kcal·mol−1 in acetonitrile. The high exergonic character of these reactions makes them irreversible. The presence of electron-withdrawing (EW) substituents in the DAA increases the activation enthalpies, in complete agreement with the experimental slowing-down of the reactions, but contrary to the Conceptual DFT prediction. Despite the nucleophilic and electrophilic character of the reagents, the global electron density transfer at the TSs indicates rather non-polar 32CA reactions. The present MEDT study establishes the depopulation of the N–N–C core in this series of DAAs with the increase of the EW character of the substituents present at the carbon center is responsible for the experimentally found deceleration.

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“…Spirocyclic compounds are molecular rings sharing a common atom; the simplest of these being bicyclic compunds. Their fascinating molecular framework and their presence in a variety of natural products are of special interest to chemists [1][2][3][4][5][6][7][8]. Within a three-dimensional fragment space, spirocycles are an essential class of molecular ring systems [5,9,10].…”

Section: Introductionmentioning

confidence: 99%

Quantum Chemical Investigation of the Formation of Spiroheterocyclic Compounds Via the (3 + 2) Cycloaddition Reaction of 1-methyl-3-(2,2,2-trifluoroethylidene)pyrrolidin-2-one with Diazomethane and Nitrone Derivatives

Pipim¹,

Tia²,

Adei³

2021

Preprint

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Spirocycles are important structures in drug development due to their inherent biological activity. Their complex architecture usually presents many synthetic difficulties which are efficiently resolved with detailed theoretical studies. The chemo-, regio- and stereoselectivities of the formation of spiroheterocyclic compounds via the (3 + 2) cycloaddition (32CA) reaction of 1-methyl-3-(2,2,2-trifluoroethylidene)pyrrolidin-2-one (A1) derivatives with diazomethane and nitrone derivative have been studied at the M06-2X/6-311G(d,p) level of theory. The reactions of diazomethane (A2) and N-methyl-C-phenyl nitrone (A3) derivatives with 1-methyl-3-(2,2,2-trifluoroethylidene)pyrrolidin-2-one derivatives (A1) occurs chemoselectively along the olefinic bond of A1 via an asynchronous one-step mechanism. Analysis of the electrophilic ( and nucleophilic ( Parr functions at the different reaction sites in A1 shows that A2 and A3 add across the atomic centers with the largest Mulliken and NBO atomic spin densities. Both electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) on the A3 molecule do not affect the observed preferred pathway in its 32CA reaction with A1 whereas the electronic and steric nature of the substituent on the A2 molecule influences the preferred pathway in the 32CA reaction of A1 and A2. The title reaction proceeds via forward electron denisity flux (FEDF), where electron density fluxes from the three-atom components (A2 and A3) to A1. The computed global electron density transfer (GEDT) values suggest that the 32CA of A1 with diazomethane is a polar reaction while the 32CA reaction of A1 with N-methyl-C-phenyl nitrone is a non-polar reaction, and an inverse relationship has been established between the polar character of the reactions and activation barriers. In all the reactions studied, the selectivities are kinetically controlled.

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Site-, enantio- and stereo-selectivities of the 1,3-dipolar cycloaddition reactions of oxanorbornadiene with C,N-disubstituted nitrones and dimethyl nitrilimines: a DFT mechanistic study

Cited by 26 publications

References 29 publications

DFT and TD-DFT calculation of new aryl cyanomethylene-quinone mono-oximes-based small molecules for organic photovoltaic

DFT and TD-DFT calculation of new aryl cyanomethylene-quinone mono-oximes-based small molecules for organic photovoltaic

Unveiling the Unexpected Reactivity of Electrophilic Diazoalkanes in [3+2] Cycloaddition Reactions within Molecular Electron Density Theory

Quantum Chemical Investigation of the Formation of Spiroheterocyclic Compounds Via the (3 + 2) Cycloaddition Reaction of 1-methyl-3-(2,2,2-trifluoroethylidene)pyrrolidin-2-one with Diazomethane and Nitrone Derivatives

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